WO2022073314A1 - Durable super-hydrophobic composite coating and preparation method therefor - Google Patents

Abstract

Disclosed in the present invention are a durable super-hydrophobic composite coating and a preparation method therefor. An ACNTB-SiO2-coupling agent suspension is applied, in parts by weight, onto the surface of a gel of a mixture of an ACNTB-SiO2-coupling agent, epoxy resin, diglycidyl ether-terminated polydimethylsiloxane, and amino-terminated hyperbranched polysiloxane, and then curing is performed to obtain the durable super-hydrophobic composite coating. The super-hydrophobic coating disclosed in the present invention has characteristics of being easy and convenient to operate and durable, and having good hydrophobicity, and the prepared coating has excellent mechanical properties and wear resistance. Particularly, in the present invention, hydrophobic nano SiO2 particles are stored in pores of ACNTB, an adhesive is decomposed in a pyrolysis mode when a coating structure is damaged, and a formed gas product can promote SiO2 to migrate to the surface of the coating to construct a new nano structure surface with exposed CNT, so that super-hydrophobic properties of the coating can be recovered.

Description

A kind of durable super-hydrophobic composite material coating and preparation method thereof technical field

The invention relates to a durable super-hydrophobic composite material coating and a preparation method thereof, in particular to a super-hydrophobic composite material coating with a micro/nano-structured surface with excellent impact resistance, friction resistance and self-healing functions and a preparation method thereof .

Background technique

Materials with superhydrophobic properties have very broad application prospects in different fields such as self-cleaning, anti-icing, anti-fog, anti-corrosion, and oil-water separation. Studies have shown that by designing complex micro/nano hierarchical structures, the superhydrophobic properties of the material surface can be achieved by introducing low surface energy species. At present, hydrophobic inorganic nanoparticles (SiO ₂ , ZnO, TiO ₂ , CNT, Al ₂ O ₃ , graphene, etc.) are often used to construct micro/nano multi-level surface structures to achieve the hydrophobicity of materials, but due to the weak interaction between inorganic nanoparticles The van der Waals interaction of the superhydrophobic coating makes the surface of the superhydrophobic coating exhibit fragile mechanical properties and tolerance, which seriously affects the superhydrophobicity of the material and greatly limits the application of superhydrophobic materials in real life. Therefore, it is a challenging task to prepare superhydrophobic coating materials with good mechanical properties and stable and durable.

Based on the above analysis, in view of the current problems and development trends in the development of superhydrophobic coating materials, improving the interaction between coating components and endowing the coating with self-healing function are important for the construction of durable and environmentally friendly superhydrophobic materials with stable structures and expansion. Its application has positive significance.

technical problem

Aiming at the problem of poor durability of the super-hydrophobic coating caused by the weak interaction between the existing inorganic particles and the particle/binder interface, the present invention combines and hybridizes a multi-level nano-particle with a stable structure with strong interaction between the particles. The micron-sized particles were combined with an epoxy system adhesive to prepare a composite superhydrophobic coating with a micro/nano-scale surface structure. The super-hydrophobic coating disclosed in the invention has the characteristics of simple operation, durability and good hydrophobicity, and the prepared coating has excellent mechanical properties and wear resistance. In particular, the hydrophobic nano _- SiO particles of the present invention are stored in the pores of _ACNTB , when the coating structure is destroyed, the adhesive is decomposed by pyrolysis, and the formed gas products can promote the migration of SiO to the surface of the coating, which is different from the exposed ones. CNTs build new nanostructured surfaces that restore the superhydrophobic properties of the coating.

technical solutions

In order to achieve the above purpose, the technical solution adopted in the present invention is:

A durable super-hydrophobic composite material coating, the preparation method of which comprises the following steps: coating ACNTB-SiO ₂ -coupling agent suspension on ACNTB-SiO ₂ -coupling agent, epoxy resin, diglycidyl ether sealant The gel surface of the mixture of terminal polydimethylsiloxane and amino-terminal hyperbranched polysiloxane is then cured to obtain a durable superhydrophobic composite coating; or the ACNTB-SiO ₂ -coupling agent suspension is coated It is coated on the surface of the gel of epoxy resin and amino-terminated hyperbranched polysiloxane mixture, and then cured to obtain a durable superhydrophobic composite coating; or the ACNTB-SiO ₂ -coupling agent suspension is coated on the ring Gel surface of a mixture of oxygen resin, diglycidyl ether-terminated polydimethylsiloxane, amino-terminated hyperbranched polysiloxane, and then cured to obtain durable superhydrophobic composite coatings; or ACNTB-SiO ₂ -Coupling agent suspension was coated on the gel surface of ACNTB-SiO ₂ -coupling agent, epoxy resin, amino-terminated hyperbranched polysiloxane mixture, and then cured to obtain durable superhydrophobic composite coating .

In the present invention, after the multi-walled carbon-oriented carbon nanotube bundle, alkali, solvent and tetraethyl orthosilicate are mixed and reacted, a silane coupling agent is added and the reaction is continued to obtain ACNTB-SiO ₂ -coupling agent.

Further, the weight ratio of multi-wall carbon-oriented carbon nanotube bundles, tetraethyl orthosilicate, silane coupling agent, alkali, and solvent is (1~2):(9~14):(2~5):(9 ~12):(100~200); among them, the multi-walled carbon oriented carbon nanotube bundles (ACNTB) have a bundle diameter of 10~25 μm and a length of 30~100 μm, with abundant pore structure, all CNTs are oriented in a certain direction and CNTs There is obvious physical entanglement between them; the silane coupling agent is γ-methacryloyloxypropyltrimethoxysilane, hexamethylsilazane, dodecyltrimethoxysilane, vinyltrimethoxysilane , phenyltrimethoxysilane or hexadecyltrimethoxysilane; the base is ammonia water or triethanolamine; the solvent is water, ethanol, ethyl acetate or a mixture thereof. The preparation method of ACNTB-SiO ₂ -coupling agent is as follows: adding ACNTB particles into an alkali solvent at room temperature, after stirring, adding a mixed solution of TEOS and solvent, reacting at 30-60°C for 18-36 hours, then adding a silane coupling agent Continue to stir for 6h to end the reaction, naturally cool to room temperature, the obtained suspension is washed with ethanol for 2~5 times, centrifuged for three times, and then dried in a vacuum oven at 60°C for 12h to obtain a black micron-sized ACNTB-coupling agent modified _SiO2 nanohybrid particles (ACNTB- _SiO2 -coupling agent), in which _SiO2 is assembled in the pore structure of ACNTB and on the surface of CNTs.

In the present invention, in the mixture, the weight parts of ACNTB-SiO ₂ -coupling agent, epoxy resin, diglycidyl ether-terminated polydimethylsiloxane, and amino-terminated hyperbranched polysiloxane are respectively 0-1 parts, 70-100 parts, 0-70 parts, 30-60 parts, wherein the amount of ACNTB-SiO ₂ -coupling agent may be 0 or not 0; diglycidyl ether-terminated polydimethylsiloxane The amount of alkane may or may not be 0; in the suspension, the weight part of the ACNTB-SiO ₂ -coupling agent is 4.0-20 parts. In the present invention, the total amount of the ACNTB-SiO ₂ -coupling agent is 4.0-20 parts, including the ACNTB-SiO ₂ -coupling agent that may be added in the gel system and the ACNTB-SiO ₂ -coupling agent in the suspension dosage.

In the present invention, the epoxy resin is bisphenol A epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, novolac epoxy resin, multifunctional glycidol One or more of ether resin, glycidyl ester epoxy resin and halogen epoxy resin; diglycidyl ether end-capped polydimethylsiloxane (DGETPDMS) is a colorless and transparent liquid with a viscosity (25°C) It is 50-10000 mPa.s, and the specific gravity (25°C) is 1.05-1.10.

In the present invention, the curing process is (50~70°C)/1h+(80~150°C)/1-2h.

The invention discloses the application of the above-mentioned durable super-hydrophobic composite material coating in the preparation of a wear-resistant hydrophobic coating; the wear-resistant hydrophobic coating has a multi-level micro/nano structure surface.

The preparation method of the durable super-hydrophobic composite material coating of the present invention is as follows: mixing epoxy resin, ACNTB-SiO ₂ -coupling agent (0-1 part), DGETPDMS (0-70 parts) and HBPSi at 30-150° C. Evenly, after maintaining for 10-20min, get the resin adhesive prepolymer tiled gel, when the prepolymer reaches the gel state, then drop the toluene suspension containing ACNTB-SiO ₂ -coupling agent on the gel The surface, after the solvent volatilizes, is cured by (50~70℃)/1h+(80~150℃)/1-2h to obtain durable superhydrophobic epoxy/ACNTB-SiO ₂ -coupling with micro/nanostructured surface agent composite coating; the weight ratio of ACNTB-SiO ₂ -coupling agent:toluene is 1:(25~50).

In the above technical solution, the ACNTB-SiO ₂ -coupling agent particles have a stable structure, and the SiO ₂ nanoparticles assembled in the pores of the micron-scale ACNTB particles can effectively transfer the load borne by the CNTs in the ACNTB, and limit the relative slip of the CNTs, otherwise, Since the SiO ₂ nanoparticles are assembled in the pore structure in ACNTB, the SiO ₂ nanoparticles are immobilized by the CNTs. The interaction between CNTs and SiO ₂ particles in the micron-sized ACNTB-SiO ₂ -coupling agent particles is restricted and confined, which enhances the interaction between CNTs and SiO ₂ , so that the micron-sized ACNTB-SiO ₂ -coupling agent particles have a stable structure .

In the above technical solution, the amine value of the amino-terminated hyperbranched polysiloxane HBPSi is 0.5-0.65 mol/100g, such as 0.59 mol/100g; the synthesis process of HBPSi can be as follows: at 60°C, mix 3-aminopropyltriethoxysilane (KH550), deionized water and absolute ethanol, stir for 4h under nitrogen protection, and cool the reaction system After reaching room temperature, a transparent liquid was obtained, and a vacuum decompression device was used to decompress the reaction system to obtain HBPSi with an amine value of 0.59 mol/100g, wherein the mass ratio of KH550, deionized water, and absolute ethanol was 22:100:16.

The superhydrophobic coating prepared by the invention has a multi-level micro/nano structure surface, the water contact angle (CA) of the surface of the superhydrophobic coating can reach 155-168°, and the rolling angle is less than 5°. In particular, the superhydrophobic coating has excellent anti-friction performance and mechanical properties. After the coating is worn for nearly 300 cycles by 800-grit sandpaper under a load of 100g (the friction stroke of one cycle is 10cm) and the impact of water pressure of 1188KPa for 120s, it still remains. Superhydrophobicity can be maintained. Due to the presence of ACNTB-SiO ₂ -coupling agent particles, the damaged coating can be partially decomposed by heat treatment, and nano-SiO ₂ easily migrates to the coating surface under the action of heat and the gas flow of decomposition products, which can be combined with CNTs New nanostructured surface that restores the superhydrophobic properties of the coating.

Oriented carbon nanotube bundles (ACNTB) are aggregates formed by many CNTs arranged in a certain direction through the action of van der Waals force and a certain physical entanglement between carbon tubes (the bundle diameter is generally micron-scale). It is relatively long and physically entangled carbon nanotubes are not easy to dissociate, but ACNTB has a rich pore structure, which makes the ACNTB structure unstable. Under the action of external force, the CNTs in ACNTB are prone to slip, and the interaction between CNTs is poor and cannot be effective. bear. In the present invention, ACNTB particles are added to an alkali solvent at room temperature, a mixed solution of TEOS and a solvent is added after stirring, a silane coupling agent is added after the reaction, the reaction is terminated after continuous stirring, and the suspension is naturally cooled to room temperature, and the obtained suspension is washed with ethanol, Centrifuge and dry to obtain black micron-scale ACNTB-coupling agent-modified SiO ₂ nano-hybrid particles (ACNTB-SiO ₂ -coupling agent), in which SiO ₂ is assembled in the pore structure of ACNTB and on the surface of CNTs, which can strengthen the The interaction between CNTs can effectively transfer the force between CNT tubes and increase the structural stability of ACNTB. As a hydrophobic particle, SiO ₂ is easily obtained by hydrolysis and modification of tetramethylsilane (TEOS). The rich pore structure of ACNTB is Sufficient conditions are prepared for the storage of superhydrophobic _SiO2 particles, and the storage of _SiO2 particles in the pores of ACNTB can not only enhance the inter-CNT interaction in ACNTB, enhance the structural stability of ACNTB, but also help maintain or improve the superhydrophobicity of ACNTB.

beneficial effect

Due to the application of the above technical solutions, the present invention has the following advantages compared with the prior art.

The super-hydrophobic coating prepared by the invention has outstanding impact resistance, is suitable for most substrate materials, and has a simple coating preparation process. Because the prepared SiO ₂ @ACNTB particles have obvious structural stability, there is a strong bond between the particles. interaction. The composite coatings thus formed have outstanding durability and superhydrophobicity stability. In addition, the damaged coating can be partially decomposed by high temperature treatment, so that _SiO2 can easily migrate to the coating surface under the action of heat and gas flow of decomposition products, and together with the exposed nanoparticles, a new type of nanostructured surface can be built, which can restore the coating. superhydrophobic properties.

Description of drawings

Figure 1 is the scanning electron microscope (SEM) and transmission electron microscope (TEM) photographs of ACNTB and ACNTB-SiO ₂ -KH570 in Example 1, wherein (a, a', c) ACNTB without ultrasonic treatment, (c') ultrasonic for 5 min Treated ACNTB, (b, b', d, d') ACNTB-SiO ₂ -KH570 after sonication for 5 min.

FIG. 2 shows the pore size distribution and particle surface area (obtained by specific surface area and porosity analyzer) of ACNTB and ACNTB-SiO ₂ -KH570 in Example 1. FIG.

Figure 3 is the water contact angle CA, rolling angle SA of the coating, digital photos of water droplets on the coating surface and SEM photos of the coating, ACNTB-SiO ₂ -KH570 (a, b, g, j), ACNTB (c, d, h, k), SiO ₂ -KH570 (e, f, i, l).

Figure 4 is the digital photo of ACNTB-SiO 2 -KH570 and ACNTB-SiO ₂ -KH570 (a) and ACNTB (b) coating water droplets on the coating surface and SEM photo of the coating after ACNTB-SiO ₂ -KH570 and ACNTB tableting.

Figure 5 shows the superhydrophobic E-51/ACNTB-SiO ₂ -KH570 composite coating prepared in Example 1, the water contact angle CA of the E-51 coating in Example 1-1 and the coating in Comparative Example 1-2 And rolling angle SA (a), coating example 1-1 (b), example 1 (c) and example 1-2 (d) SEM pictures of the coating.

Figure 6 shows the CA and SA (a) of the superhydrophobic E-51/ACNTB-SiO ₂ -KH570 composite coating prepared in Example 1 after being impacted by different water flows for 120 s. The surface of the coating was impacted by a water pressure of 1329 KPa. SEM image (b).

Figure 7 shows the superhydrophobic E-51/ACNTB-SiO ₂ -KH570 composite coating prepared in Example 1 after being subjected to different impact energies of sand particles (250 g, with an average particle size of 251 μm) for the composite coatings CA and SA (a). SEM image of the coated surface after impact with a single sand particle impact energy of 1.04×10 ^-7 J/grain (b).

Figure 8 shows the CA and SA (a) and coating friction cycles 2 (b), 60 of the superhydrophobic E-51/ACNTB-SiO ₂ -KH570 composite coating prepared in Example 1 after sanding with 800-grit sandpaper under a load of 100 g. (c), SEM images of 260(d) and 300(e) after rubbing.

Figure 9 is the water contact angle photo and SEM of the superhydrophobic E-51/ACNTB-SiO ₂ -KH570 composite prepared in Example 1 after the coating is damaged and the tape is peeled off and after being placed in a 300 ℃ muffle furnace for 9 h Photographs, where a, b, and d correspond to the heated coating after damage and peeling; c corresponds to the unheated coating after damage and peeling.

FIG. 10 is SEM photographs of the coatings in Example 2 and Comparative Example 2. FIG.

Embodiments of the present invention

The raw materials involved in the present invention are all conventional commercial products, and the specific operation methods and testing methods involved are all conventional conditions unless otherwise specified; the technical solutions of the present invention are further described below in conjunction with the accompanying drawings and examples.

In the examples and comparative examples, the bundle diameter of the multi-walled carbon oriented carbon nanotube bundle (ACNTB) is 10-25 μm, and the length is 30-100 μm.

Synthesis example.

At 60 °C, 3-aminopropyltriethoxysilane (KH550), deionized water and absolute ethanol were mixed, stirred for 4 h under nitrogen protection, and then the reaction system was cooled to room temperature to obtain a transparent liquid, using vacuum The decompression device decompresses the reaction system to remove the solvent to obtain HBPSi with an amine value of 0.59 mol/100g, wherein the weight ratio of KH550, deionized water and absolute ethanol is 22:100:16.

Example 1 .

Under stirring conditions, 1.0g of ACNTB particles was added to the mixed solution of 9.1g of ammonia water and 110g of ethanol. After stirring for 10min, the mixed solution of 9.35g of TEOS and 40g of ethanol was added dropwise, heated in a water bath at 60°C, and 2.5g was added after stirring for 18h. g of KH570, after continuing to stir for 6 h, the reaction was completed, naturally cooled to room temperature, the obtained suspension was washed with ethanol and centrifuged three times to collect ACNTB-SiO ₂ -KH570 particles, and then dried in a vacuum oven at 60 °C for 12 h to obtain black ACNTB -SiO2 _- KH570 particles.

1 is a scanning electron microscope (SEM) and a transmission electron microscope (TEM) photograph of ACNTB, ACNTB-SiO ₂ -KH570 in Example 1 of the present invention. It can be seen from Figures 1a, 1a' and 1c that the CNTs in ACNTB have a certain orientation arrangement, and there are obvious entanglements between the CNTs, in addition, ACNTB has a rich pore structure, but as can be seen from Figure 1c', After ultrasonic treatment, the structural integrity of ACNTB is obviously damaged, and the CNTs are easily dissociated; from Figure 1b, 1b', 1d and 1d', it can be seen that in the ultrasonically treated ACNTB-SiO ₂ -KH570, the surface of the carbon tube not only adsorbs There are nano-SiO ₂ particles, and nano-SiO ₂ is embedded between the carbon tubes and the gaps between the carbon tubes. The overall structure of ACNTB-SiO ₂ -KH570 is complete. It can be seen that the ACNTB-SiO ₂ -KH570 particle structure system constructed by the hybridization of nano-SiO ₂ and ACNTB is stable and not easy to be broken under the action of external force. Figure 2 shows the pore size distribution and particle surface area of ACNTB and ACNTB-SiO ₂ -KH570 in Example 1. It can be seen from Figure 2 that due to the assembly of SiO ₂ in the pores of ACNTB, the pores of ACNTB-SiO ₂ -KH570 are significantly reduced. The pores become smaller, but the specific surface area of ACNTB-SiO ₂ -KH570 is larger than that of ACNTB, which indicates that the interaction area between ACNTB-SiO ₂ -KH570 particles and other components of the coating increases, which is beneficial to improve the interaction between them.

In order to evaluate the superhydrophobicity of ACNTB-SiO ₂ -KH570 particles, ACNTB-SiO ₂ -KH570 particles and toluene were prepared into an ACNTB-SiO ₂ -KH570 solution with a mass ratio of 1:9, and the solution was drop-coated onto a glass slide On the surface of the glass slide, a dense layer of ACNTB-SiO ₂ -KH570 particles was formed on the surface of the glass slide, and the solvent was evaporated to dryness in an oven at 60 °C and then treated for 1 h to obtain an ACNTB-SiO ₂ -KH570 coating. Methods ACNTB and SiO ₂ -KH570 particles were drop-coated on the glass slide surface to obtain ACNTB and SiO ₂ -KH570 coatings as comparative samples. Figure 3 is the water contact angle (CA), rolling angle (SA), digital photos and SEM photos of ACNTB-SiO ₂ -KH570, ACNTB and SiO ₂ -KH570 coatings. The CA and SA values of the ACNTB coatings are respectively 155.7±2.5° and 2.5±0.5°. The CA and SA values of the SiO ₂ -KH570 coating are 152.7±3° and 4±0.5°, respectively. The CA and SA values of the ACNTB-SiO ₂ -KH570 coating were 166.3±1° and 1.8±0.5°, respectively. Obviously, the ACNTB-SiO ₂ -KH570 coating has higher CA and lower SA values than the ACNTB and SiO ₂ -KH570 coatings, indicating that the ACNTB-SiO ₂ -KH570 coating has good superhydrophobic properties. For superhydrophobic surfaces, air pockets between droplets and solids can form a stable liquid-gas-solid interface, and solid surfaces with complex hierarchical structures can increase the gas fraction on the surface and provide more stable air pockets, giving materials better hydrophobicity. The SEM image of ACNTB-SiO ₂ -KH570 (Fig. 1) shows that ACNTB-SiO ₂ -KH570 particles are composed of ACNTB and SiO ₂ -KH570 particles, which have a complex hierarchical nanostructured surface, so they can have excellent superhydrophobicity sex. Among them, under stirring conditions, a mixed solution of 9.35 g of TEOS and 40 g of ethanol was added dropwise to the mixed solution of 9.1 g of ammonia water and 110 g of ethanol, heated in a water bath at 60°C, and 2.5 g of KH570 was added after stirring for 18 h. After the reaction was completed, it was naturally cooled to room temperature, and the obtained suspension was washed with ethanol and centrifuged three times to collect the particles, and then dried in a vacuum oven at 60° C. for 12 hours to obtain nano-SiO ₂ -KH570 particles.

Figure 4 is a digital photo of the ACNTB-SiO ₂ -KH570 and ACNTB flakes obtained by conventional compression of the ACNTB-SiO ₂ -KH570 and ACNTB coatings by a press, the water droplets on the coating surface and the SEM photo after pressing. The CAs of water in ACNTB-SiO ₂ -KH570 and ACNTB flakes are 147.4±2.5° and 71.7±2.5°, respectively. Apparently, the pressed ACNTB-SiO ₂ -KH570 sheet material is still hydrophobic. It can be seen from the SEM image (Fig. 4a) that the compressed ACNTB-SiO ₂ -KH570 sheet still has many pore structures; while the pores between the CNTs in the compressed ACNTB are significantly reduced. Since the existence of SiO ₂ particles between CNTs in ACNTB-SiO ₂ -KH570 can maintain the spacing between CNTs and limit the displacement of CNTs, the original structure can be relatively well maintained, which indicates that the ACNTB-SiO ₂ -KH570 coating Good structural stability.

At 30°C, 2g epoxy resin (E-51), 0.02g ACNTB-SiO ₂ -KH570, 0.6g DGETPDMS (colorless transparent liquid, viscosity (25°C) 5000 mPa.s, specific gravity (25°C) 1.08 ) and 0.88g HBPSi were mixed evenly, and maintained for 10 minutes to obtain a resin adhesive prepolymer, and then the adhesive prepolymer was uniformly scraped on the surface of the aluminum plate substrate (the thickness of the adhesive prepolymer layer was 70 μm), and the prepolymer reached solidification after 15 minutes. In the glue state, the toluene suspension containing ACNTB-SiO ₂ -KH570 (ACNTB-SiO ₂ -KH570, toluene was 0.086g, 4.3g, respectively) was drop-coated on the surface of the resin prepolymer, placed for 30 minutes, after 60 ℃/1h+100℃/1h curing treatment to obtain durable super-hydrophobic E-51/ACNTB-SiO ₂ -KH570 composite coating with micro/nano-structured surface, which is durable super-hydrophobic composite coating, coating thickness is 100 μm.

The following comparative example 1-1, comparative example 1-2, and comparative example 1-3 are in order to be compared with the examples to reflect the unexpected technical effects of the present invention.

Comparative ratio 1-1 .

At 30°C, mix 2g epoxy resin (E-51), 0.6g DGETPDMS (colorless transparent liquid, viscosity (25°C) 5000 mPa.s, specific gravity (25°C) 1.08), 0.88g HBPSi, and keep for 10min After that, the resin adhesive prepolymer is obtained, and then the adhesive prepolymer is uniformly scraped and coated on the surface of the aluminum plate substrate. When the prepolymer reaches a gel state, E-51 is obtained by curing at 60°C/1h+100°C/1h. Coating, the coating thickness is 100μm.

Comparative ratio 1-2 .

At 30°C, 2g epoxy resin (E-51), 0.02g ACNTB-SiO ₂ -KH570, 0.6g DGETPDMS (colorless transparent liquid, viscosity (25°C) 5000 mPa.s, specific gravity (25°C) 1.08 ) and 0.88g HBPSi were mixed evenly, and maintained for 10min to obtain a resin adhesive prepolymer, which was blended with ACNTB-SiO ₂ -KH570 toluene suspension (ACNTB-SiO ₂ -KH570:toluene=0.086g:4.3g), and then scraped It was coated on the surface of the substrate, and when the prepolymer reached a gel state, the E-51/ACNTB-SiO ₂ -KH570-blend coating was obtained by curing at 60°C/1h+100°C/1h, and the coating thickness was 100 μm.

Figure 5 shows the superhydrophobic E-51/ACNTB-SiO ₂ -KH570 composite coating prepared by water droplets in Example 1, the E-51 coating of Comparative Example 1-1 and the E-51/ACNTB of Comparative Example 1-2 -Water contact angle CA and rolling angle SA values on SiO ₂ -KH570-blend coating, SEM photograph of coating surface. The CA and SA of the coating in Example 1 are: 159° and 2.5°, respectively. It can be seen that the E-51/ACNTB-SiO ₂ -KH570 composite coating in Example 1 has excellent superhydrophobicity compared to the coatings of Comparative Examples 1-1 and 1-2. From the SEM photo of Figure 5c, it can be seen that the E-51/ACNTB-SiO ₂ -KH570 composite coating has micro-protrusions, and the existence of nano-CNT and SiO ₂ particles can be clearly observed on the surface of the coating. E-51/ACNTB The micro/nano-structured surface of the -SiO ₂ -KH570 composite coating is conducive to adsorbing a large number of air molecules, reducing the contact between water droplets and the coating surface, so that the coating exhibits excellent superhydrophobicity; while Comparative Example 1 The -1 and Comparative Examples 1-2 coatings have low CA and high SA values.

Figure 6 is the SEM images of the superhydrophobic E-51/ACNTB-SiO ₂ -KH570 composite coating prepared in Example 1 after different water flow impact (120s) and the surface SEM images of the coating after impact with water pressure of 1329KPa. It can be found from Fig. 6a that although the CA of the EP/ACNTB-SiO ₂ -KH570 coating decreased slightly and the SA value gradually increased after being impacted by different water pressures, the EP/ACNTB-SiO ₂ after being washed by a water pressure of 1188KPa for 120 s - The CA value of the KH570 coating was 151.4±1.5°, and the SA value remained at 7.1±1.5°. After the coating was impacted by water pressure of 1329KPa, the CA decreased to 147.7±1.5°, and the SA increased from 2.5±0.5° to 14.3±3°. At this time, the superhydrophobicity of the coating may disappear, but it still has a high Hydrophobicity. It can be seen from Figure 6b that after the pressure shock of 1329KPa, the exposed CNTs can be clearly observed on the surface of the coating, and a large number of exposed particles can effectively ensure the hydrophobicity of the coating.

Figure 7 shows the superhydrophobic E-51/ACNTB-SiO ₂ ^-KH570 composite coating prepared in Example 1 after being subjected to different impact energies of sand particles (average particle size of 251 μm). SEM image of the coating surface after J/grain energy impact. As the impact energy of quartz sand increases, the CA and SA values of the composite coatings after impact slowly decrease and increase, respectively. When the impact energy is 1.04×10 ^-7 J/grain, the coating CA is 151.3±1.6°, and the SA is 11.5±1.9°, indicating that the coating also exhibits good impact resistance to sand impact. After being impacted by sand particles at 1.04×10 ^-7 J/grain, the damaged area of the composite coating can still maintain a good rough surface structure, and protruding nanoparticles can be observed on the surface, which is conducive to the maintenance of superhydrophobicity. played a positive role. When the impact energy reaches 1.3×10 ^-7 J/grain, the CA and SA of the coating are 125.7±2° and 45.2±2.9°, respectively, and the superhydrophobic properties are lost.

The water impact test (Fig. 6) and the falling sand test (Fig. 7) show that the composite coating in Example 1 has excellent impact resistance with excellent strength and toughness, and strong interactions between particles may be effective Resisting external forces, it has played a positive role in prolonging the service life of the coating.

Fig. 8 is the change of CA and SA of the superhydrophobic E-51/ACNTB-SiO ₂ -KH570 composite coating prepared in Example 1 after grinding with 800-grit sandpaper under 100 g load and the SEM photograph of the coating surface. It can be seen from the figure that when the coating undergoes 2 friction cycles, the CA of the coating increases and the SA slightly decreases; it can be seen from Figure 8b that there are obviously prominent CNTs on the surface of the coating, and this surface structure can make The adsorption of air molecules on the coating surface increases, reducing the contact of water droplets with the coating surface. Especially, when the rubbing cycles reached 260 times, the CA and SA of the coating remained above 150° and below 10°, indicating that the coating was still superhydrophobic, and the coating surface was still rich in nanoparticles at this time. The E-51/ACNTB-SiO ₂ -KH570 composite coating of the present invention can withstand nearly 300 sandpaper grinding cycles (the coating has a friction stroke of nearly 30 m on the surface of the sandpaper), indicating that the coating has excellent wear resistance. The main reason is It is because the coating has excellent mechanical properties and has a large force with the adhesive layer, so that the coating can effectively resist external wear.

Compared with the superhydrophobic coatings reported in the existing literature, the superhydrophobic E-51/ACNTB-SiO ₂ -KH570 composite coating prepared in Example 1 has the following advantages: (1) It does not contain fluorine, and the coating is green Environmental protection; (3) The superhydrophobic coating has both high impact resistance and friction performance. Among the coatings reported in the literature, no water impact pressure reaches 1188KPa, and the sand impact energy reaches 1.04×10 ^-7 J/grain. Coatings that maintain superhydrophobicity and have high impact properties have also been reported to have superhydrophobic properties after nearly 300 sandpapering cycles.

The superhydrophobic E-51/ACNTB-SiO ₂ -KH570 composite coating prepared in Example 1 was polished with 800-grit sandpaper for 300 times under a load of 100 g and then peeled off with 3M tape (removing the surface particle floating layer) to obtain a damaged coating; then It was placed in a muffle furnace at 300 °C for 9 h, and the water contact angle photos and SEM photos of the coating surface before and after heating were tested, as shown in Figure 9. The coating of E-51/ACNTB-SiO ₂ -KH570 composite was damaged and lost its hydrophobicity after the tape was peeled off. After heating at 300 °C for 9 h, the CA of the coating changed from 123° to 160.4±2.5°, and the SA was less than 1°. It can be seen from the SEM photos that after the damaged coating is heated at 300 °C, nanoparticles are aggregated on the surface of the coating, and this structure is beneficial to the recovery of the superhydrophobic property of the coating.

Comparative ratio 1-3 .

At 30°C, 2g epoxy resin (E-51), 0.02g ACNTB-SiO ₂ -KH570, 0.6g DGETPDMS (colorless transparent liquid, viscosity (25°C) 5000 mPa.s, specific gravity (25°C) 1.08 ) and 0.88g of 3-aminopropyltriethoxysilane (KH550) were mixed evenly, and maintained for 10min to obtain a resin adhesive prepolymer, and then the adhesive prepolymer was uniformly scraped on the surface of the aluminum plate substrate. After 15min, the prepolymer was When the gel state was reached, the toluene suspension containing ACNTB-SiO ₂ -KH570 (ACNTB-SiO ₂ -KH570, toluene was 0.086g, 4.3g respectively) was drop-coated on the surface of the resin prepolymer, and after standing for 30 minutes, E-51/KH550/ACNTB-SiO ₂ -KH570 composite coating with micro/nano-structured surface was obtained after curing at 60℃/1h+100℃/1h. After water pressure 1188KPa/120s, sand impact energy 1.04× After 10 ^-7 J/grain and 50 sandpaper rubbing cycles, it did not have superhydrophobicity (CA<130°, SA>15°).

Comparative ratio 1-4 .

At 30°C, 2g epoxy resin (E-51), 0.02g ACNTB-SiO ₂ -KH570, 0.6g DGETPDMS (colorless transparent liquid, viscosity (25°C) 5000 mPa.s, specific gravity (25°C) 1.08 ) and 0.88g HBPSi were mixed evenly, and maintained for 10 minutes to obtain a resin adhesive prepolymer, and then the adhesive prepolymer was uniformly scraped on the surface of the aluminum plate substrate (the thickness of the adhesive prepolymer layer was 70 μm), and the prepolymer reached solidification after 15 minutes. In the glue state, it was cured at 60°C/1h+100°C/1h, and then dripped with a toluene suspension containing ACNTB-SiO ₂ -KH570 (ACNTB-SiO ₂ -KH570 and toluene were 0.086g and 4.3g, respectively), and left for 30 minutes. Minutes later, the coating was obtained by curing treatment at 60℃/1h+100℃/1h, and it did not have hydrophobicity (CA<120°, SA>35°) after 1 sandpaper rubbing.

In summary, the superhydrophobic epoxy composite coating prepared by using the superhydrophobic ACNTB-SiO ₂ -KH570 particles formed by the hybridization of multi-level nanoparticles with stable structure has excellent durability.

Example 2 .

Under stirring conditions, 1.0 g of ACNTB particles were added to the mixed solution of 9.1 g of ammonia water and 110 g of ethanol. After stirring for 10 min, a mixed solution of 9.35 g of TEOS and 40 g of ethanol was added dropwise, heated in a water bath at 60 °C, stirred at a constant speed for 18 h, and then added with 2.5 g of ethanol. g of KH570, after continuing to stir for 6 h, the reaction was completed, naturally cooled to room temperature, the obtained suspension was washed with ethanol and centrifuged three times to collect ACNTB-SiO ₂ -KH570 particles, and then dried in a vacuum oven at 60 °C for 12 h to obtain black ACNTB -SiO2 _- KH570 particles.

At 30°C, 2g epoxy resin (E-51), 0.02g ACNTB-SiO ₂ -KH570, 0.6g DGETPDMS (colorless transparent liquid, viscosity (25°C) 5000 mPa.s, specific gravity (25°C) 1.08 ) and 0.88g HBPSi were mixed evenly and maintained for 10 minutes to obtain a resin adhesive prepolymer, and then the adhesive prepolymer was uniformly scraped on the surface of the aluminum plate substrate (the thickness of the adhesive prepolymer coating was 70 μm), and the prepolymer reached 15 minutes later. In the gel state, the ACNTB-SiO ₂ -KH570-toluene suspension (ACNTB-SiO ₂ -KH570: toluene = 0.114g: 5.7g) containing ACNTB-SiO 2 -KH570-toluene suspension was drop-coated on the surface of the resin prepolymer. ℃/1h+100℃/1h curing treatment obtained durable superhydrophobic E-51/ACNTB-SiO ₂ -KH570 composite coating with micro/nano structured surface, and the coating thickness was 100 μm.

Comparative ratio 2-1 .

At 30°C, 2g epoxy resin (E-51), 0.02g ACNTB-SiO ₂ -KH570, 0.6g DGETPDMS (colorless transparent liquid, viscosity (25°C) 5000 mPa.s, specific gravity (25°C) 1.08 ) and 0.88g HBPSi were evenly mixed, and after maintaining for 10min, the resin adhesive prepolymer was obtained, which was blended with ACNTB-SiO ₂ -KH570 suspension (ACNTB-SiO ₂ -KH570: solvent=0.4g:18g), and then scraped on the The surface of the substrate was cured at 60°C/1h+100°C/1h to obtain an E-51/ACNTB-SiO ₂ -KH570-blend coating with a coating thickness of 100 μm.

10 is the SEM photos of the coatings in Example 2 and Comparative Example 2-1, and Table 1 is the performance data of the coatings in Example 2 and Comparative Example 2-1; the test method is the same as that in Example 1. As can be seen from Figure 10 and Table 1, the present invention adopts a small amount of ACNTB-SiO ₂ -KH570 particles to obtain super-hydrophobicity of the coating, and the coating surface has a micro/nano-structured surface. The blending technology needs to add a large amount of ACNTB-SiO ₂ -KH570 particles to obtain a higher CA, but the SA is obviously greater than 10°, and the coating does not have superhydrophobicity. It can be seen from Table 1 that the coating in Example 2 has super-hydrophobicity after being subjected to water pressure of 1188KPa, sand impact energy of 1.04×10 ^-7 J/grain and 250 sandpaper friction cycles, and the coating can be damaged at 300° after being damaged. C heating for 9h restores the superhydrophobicity.

.

Comparative ratio 2-2 .

Under stirring conditions, a mixed solution of 9.35 g of TEOS and 40 g of ethanol was added dropwise to the mixed solution of 9.1 g of ammonia water and 110 g of ethanol, heated in a water bath at 60 °C, stirred at a constant speed for 18 h, and then added with 2.5 g of KH570, and continued to stir for 6 h to complete the reaction. , cooled to room temperature naturally, the obtained suspension was washed with ethanol and centrifuged three times to collect the particles, and then dried in a vacuum oven at 60 °C for 12 h to obtain SiO ₂ -KH570 particles.

At 30°C, 2g epoxy resin (E-51), 0.02g SiO ₂ -KH570, 0.6g DGETPDMS (colorless transparent liquid, viscosity (25°C) 5000 mPa.s, specific gravity (25°C) 1.08), 0.88g of HBPSi was mixed evenly and maintained for 10 minutes to obtain a resin adhesive prepolymer. Then the adhesive prepolymer was uniformly scraped on the surface of the aluminum plate substrate (the thickness of the adhesive prepolymer layer was 70 μm), and the prepolymer reached a gel state after 15 minutes. , then drop-coat the surface of the resin prepolymer with SiO ₂ -KH570-toluene suspension (SiO ₂ -KH570: toluene = 0.114g: 5.7g), and after standing for 30 minutes, the temperature is 60℃/1h+100℃/ The E-51/SiO ₂ ^-KH570 composite coating (coating thickness of 100 μm) was obtained by curing for 1 h. None of them have superhydrophobicity (CA<130°, SA>15°).

Comparative ratio 2-3 .

Under stirring conditions, 0.2 g of KH570 was added dropwise to the mixed solution of 10 g of ACNTB particles and 100 g of ethanol at 60 °C. After stirring for 6 h, the reaction was completed, and the suspension was naturally cooled to room temperature. The obtained suspension was washed with ethanol and centrifuged three times. The particles were collected and then dried in a vacuum oven at 60 °C for 12 h to obtain ACNTB-KH570 particles.

At 30°C, 2g epoxy resin (E-51), 0.02g ACNTB-KH570, 0.6g DGETPDMS (colorless transparent liquid, viscosity (25°C) 5000 mPa.s, specific gravity (25°C) 1.08), 0.88 The gHBPSi was evenly mixed and maintained for 10 minutes to obtain a resin adhesive prepolymer, and then the adhesive prepolymer was uniformly scraped on the surface of the aluminum plate substrate (the thickness of the adhesive prepolymer layer was 70 μm). After 15 minutes, when the prepolymer reached a gel state , and then drop-coated the ACNTB-KH570-toluene suspension (ACNTB-KH570: toluene = 0.114g:5.7g) on the surface of the resin prepolymer, placed for 30 minutes, and cured at 60°C/1h+100°C/1h The E-51/ACNTB-KH570 composite coating (coating thickness of 100 μm) was obtained, which did not have superimposition after the water pressure of 1188KPa/120s, the sand impact energy of 1.04×10 ^-7 J/grain and 30 sandpaper friction cycles. Hydrophobicity (CA<110°, SA>35°).

In summary, the superhydrophobic epoxy composite coating prepared by using the superhydrophobic ACNTB-SiO ₂ -KH570 particles formed by the hybridization of multi-level nanoparticles with stable structure has excellent durability.

Example 3 .

Under stirring conditions, 2.0 g of ACNTB particles were added to the mixed solution of 12 g of ammonia water and 150 g of ethanol. After stirring for 10 min, the mixed solution of 14 g of TEOS and 50 g of ethanol was added dropwise, heated in a water bath at 60 °C, and 5 g of ethanol was added after stirring for 36 h. Vinyltriethoxysilane (VTES), after stirring for 6 h, the reaction was completed, and the suspension was naturally cooled to room temperature. The obtained suspension was washed with ethanol and centrifuged three times to collect ACNTB-SiO ₂ -VTES particles, and then placed in a vacuum oven at 60 °C. After drying in medium for 12 h, black ACNTB-SiO ₂ -VTES particles were obtained.

At 80°C, 2g epoxy resin (E-44) and 0.6g HBPSi were mixed uniformly and maintained for 20min to obtain a resin adhesive prepolymer, and then the adhesive prepolymer was uniformly scraped on the surface of the aluminum plate substrate (adhesive prepolymer The layer thickness is 70 μm), and when the prepolymer reaches a gel state, the ACNTB-SiO ₂ -VTES-toluene suspension (ACNTB-SiO ₂ -VTES: toluene = 0.08g: 2g) prepared in advance is gradually added. It was coated on the surface of the resin prepolymer, and after the solvent was evaporated, the durable superhydrophobic E-44/ACNTB-SiO ₂ -VTES composite material with micro/nano structure surface was obtained by curing at 50℃/1h+80℃/2h. layer with a coating thickness of 100 μm.

Comparative ratio 3-1 .

At 80°C, 2g epoxy resin (E-44) and 0.6g HBPSi were mixed uniformly and maintained for 20min to obtain a resin adhesive prepolymer, which was mixed with ACNTB-SiO ₂ -VTES suspension (ACNTB-SiO ₂ -VTES: solvent = 0.08g:2g) after blending, then blade coating on the surface of the substrate, and curing at 50°C/1h+80°C/2h to obtain E-44/ACNTB-SiO ₂ -VTES-blend coating with a coating thickness of 100 μm .

Table 2 is the performance data of the coatings in Example 3 and Comparative Example 3. As can be seen from Table 2, when using the same small amount of ACNTB-SiO ₂ -VTES particles, the composite coating prepared by the technology of the present invention can obtain excellent superhydrophobicity, while the coating obtained by the blending technology has excellent superhydrophobicity. CA is lower than 150°, SA is obviously greater than 10°, and the coating does not possess superhydrophobicity. It can be seen from Table 2 that the coating in Example 3 has super-hydrophobicity after being subjected to water pressure of 1188KPa/120s, sand impact energy of 1.04×10 ^-7 J/grain and 300 sandpaper friction cycles. Heating at 300 °C for 9 h restores the superhydrophobicity.

.

Comparative ratio 3-2 .

Under stirring conditions, a mixed solution of 14 g of TEOS and 50 g of ethanol was added dropwise to the mixed solution of 12 g of ammonia water and 150 g of ethanol, heated in a water bath at 60 °C, and 5 g of vinyltriethoxysilane (VTES) was added after conventional stirring for 36 h. After stirring for 6 hours, the reaction was completed, and the mixture was naturally cooled to room temperature. The obtained suspension was washed with ethanol and centrifuged three times to collect SiO ₂ -VTES particles, and then dried in a vacuum oven at 60°C for 12 hours to obtain SiO ₂ -VTES particles.

At 80°C, 2g epoxy resin (E-44) and 0.6g HBPSi were mixed uniformly and maintained for 20min to obtain a resin adhesive prepolymer, and then the adhesive prepolymer was uniformly scraped on the surface of the aluminum plate substrate (adhesive prepolymer The layer thickness is 70 μm), and when the prepolymer reaches a gel state, the pre-prepared SiO ₂ -VTES-toluene suspension (SiO ₂ -VTES: toluene=0.08g:2g) is gradually dripped onto the resin pre-polymer. The polymer surface, after the solvent volatilized, was cured at 50°C/1h+80°C/2h to obtain an E-44/SiO ₂ -VTES composite coating (coating thickness 100 μm). Sand impact energy of 1.04×10 ^-7 J/grain and 70 sandpaper friction cycles did not have superhydrophobicity (CA<140°, SA>10°).

In summary, the superhydrophobic epoxy composite coating prepared by using the superhydrophobic ACNTB-SiO ₂ -VTES particles formed by the hybridization of multi-level nanoparticles with stable structure has excellent durability.

Example 4 .

Under stirring conditions, 1.2 g of ACNTB particles were added to the mixed solution of 9 g of ammonia water and 90 g of ethanol. After stirring for 10 min, the mixed solution of 9.0 g of TEOS and 10 g of ethanol was added dropwise, heated in a water bath at 60 °C, and 2 g of ethanol was added after stirring at a constant speed for 18 h. Dodecyltrimethoxysilane (DTMS), after stirring for 6 h, the reaction was completed, naturally cooled to room temperature, the obtained suspension was washed with ethanol and centrifuged three times to collect ACNTB-SiO ₂ -DTMS particles, and then at 60 °C After drying in a vacuum oven for 12 h, black ACNTB-SiO ₂ -DTMS particles were obtained.

At 50 °C, 1.4g of phenolic epoxy resin (F51), 1.4g of DGETPDMS and 1.2g of HBPSi were mixed uniformly, and a resin adhesive system was obtained after 20 minutes, and then the adhesive system was uniformly scraped on the surface of the aluminum plate substrate (the thickness of the adhesive prepolymer layer is 70 μm), when the system reaches the gel state, the pre-prepared ACNTB-SiO ₂ -DTMS-toluene suspension (ACNTB-SiO ₂ -DTMS: toluene = 0.4g:20g) is gradually dripped onto the resin prepolymer. The surface, after the solvent volatilized, was cured at 70°C/1h+150°C/1h to obtain a F51/ACNTB-SiO ₂ -DTMS composite coating with a coating thickness of 100 μm.

Comparative ratio 4-1 .

At 50 °C, 2 g epoxy resin (F51), 1.4 g DGETPDMS, 1.2 g HBPSi were mixed uniformly, and after 20 min, a resin adhesive prepolymer was obtained, which was mixed with ACNTB-SiO ₂ -DTMS suspension (ACNTB-SiO ₂ -DTMS: solvent = 0.4 g: 20g) after blending, then blade coating on the surface of the substrate, and curing at 70°C/1h+150°C/1h to obtain a F51/ACNTB-SiO ₂ -DTMS coating with a coating thickness of 100 μm.

Table 3 is the coating performance data in Example 4 and Comparative Example 4-1. It can be seen from Table 3 that with the same content of ACNTB-SiO ₂ -DTMS particles, the coating can obtain excellent superhydrophobicity by using the technology of the present invention; while the coating using the blending technology can obtain a CA lower than 150°, The SA is significantly greater than 10°, and the coating does not possess superhydrophobicity. It can be seen from Table 3 that the coating in Example 4 has superhydrophobicity after being subjected to water pressure of 1188KPa/120s, sand impact energy of 1.04×10 ^-7 J/grain and 250 sandpaper friction cycles. Heating at 320°C for 5h restores the superhydrophobicity.

.

Comparative ratio 4-2 .

Under stirring conditions, a mixed solution of 9.0 g of TEOS and 10 g of ethanol was added dropwise to the mixed solution of 9 g of ammonia water and 90 g of ethanol, heated in a water bath at 60 °C, stirred at a constant speed for 18 h, and then added with 2 g of dodecyltrimethoxysilane (DTMS). ), after stirring for 6 h, the reaction was completed, and the suspension was naturally cooled to room temperature. The obtained suspension was washed with ethanol and centrifuged three times to collect the particles, and then dried in a vacuum oven at 60 °C for 12 h to obtain SiO ₂ -DTMS particles.

Under stirring conditions, 10 g of ACNTB particles were added to 90 g of ethanol, and after stirring for 10 min, 0.5 g of dodecyltrimethoxysilane (DTMS) was added under heating in a 60°C water bath, and after continuing to stir for 6 h, the reaction was over, and it was cooled naturally. After reaching room temperature, the obtained suspension was washed with ethanol and centrifuged three times to collect the particles, and then dried in a vacuum oven at 60 °C for 12 h to obtain ACNTB-DTMS particles.

At 50 °C, 1.4g of phenolic epoxy resin (F51), 1.4g of DGETPDMS and 1.2g of HBPSi were mixed uniformly, and a resin adhesive system was obtained after 20 minutes, and then the adhesive system was uniformly scraped on the surface of the aluminum plate substrate (the thickness of the adhesive prepolymer layer is 70 μm), and when the system reaches the gel state, add the ACNTB-DTMS/SiO ₂ -DTMS/toluene suspension prepared in advance (the weights of ACNTB-DTMS, SiO ₂ -DTMS, toluene are 0.2 g, 0.2 g, 20g) was gradually dripped on the surface of the resin prepolymer. After the solvent was evaporated, the composite coating was obtained by curing at 70°C/1h+150°C/1h. The thickness of the coating was 100 μm. Impact energy of 1.04×10 ^-7 J/grain and 20 sandpaper rubbing cycles did not show superhydrophobicity (CA<130°, SA>20°).

To sum up the above analysis, the superhydrophobic epoxy composite coating prepared by using ACNTB-SiO ₂ -DTMS particles formed by multi-level nanoparticle hybridization has excellent durability.

To ensure that _SiO2 can transfer loads efficiently, _SiO2 must be effectively embedded in the pores of ACNTB. In the present invention, there is a strong interaction between CNT and SiO ₂ , so that SiO ₂ can effectively transfer the load, thereby effectively enhancing the structural stability of ACNTB, and ensuring that the subsequently synthesized coating has stable mechanical properties and superhydrophobic performance stability. Further, the pores in ACNTB can be used as micro-reaction vessels or mold cavities, which are favorable for the infiltration of TEOS and in-situ hydrolysis to generate nano _- SiO embedded in the pores. At this time, the SiO particles are confined in the pore structure, and when the _ACNTB is stressed, , SiO ₂ can transfer loads between CNTs and improve the bearing force of ACNTB particles. There is a strong interaction between nanoparticles in the ACNTB-SiO ₂ system, that is, the ACNTB-SiO ₂ system particles with a stable structure can improve the microscopic stability of the coating. More interestingly, the ACNTB-SiO ₂ system basically retains the high aspect ratio of the original ACNTB, which is easily oriented along the fluid direction driven by the gravitational field and hydrodynamic force, and is constructed with a special surface structure coating. Since _SiO2 is embedded in the pores of ACNTB, the specific surface area of the ACNTB- _SiO2 particles per unit volume is also much larger than that of the ACNTB particles. Therefore, the interaction between the ACNTB- _SiO2 particles and the adhesive will be enhanced, which is beneficial to the stability of the superhydrophobic coating. improvement.

Claims (10)

1. A durable super-hydrophobic composite coating, characterized in that the preparation method of the durable super-hydrophobic composite coating comprises the following steps: coating ACNTB-SiO ₂ -coupling agent suspension on ACNTB-SiO ₂ - Gel surface of a mixture of coupling agent, epoxy resin, diglycidyl ether-terminated polydimethylsiloxane, amino-terminated hyperbranched polysiloxane, and then cured to give a durable superhydrophobic composite coating ; or coating the ACNTB-SiO ₂ -coupling agent suspension on the gel surface of epoxy resin, amino-terminated hyperbranched polysiloxane mixture, and then curing to obtain a durable super-hydrophobic composite coating; or ACNTB-SiO ₂ -coupling agent suspension is coated on the surface of the gel of epoxy resin, diglycidyl ether-terminated polydimethylsiloxane, and amino-terminated hyperbranched polysiloxane mixture, and then cured to obtain Durable superhydrophobic composite coating; or coating ACNTB-SiO ₂ -coupling agent suspension on a gel of ACNTB-SiO ₂ -coupling agent, epoxy resin, amino-terminated hyperbranched polysiloxane mixture surface, and then cured, resulting in a durable superhydrophobic composite coating.
2. The durable super-hydrophobic composite material coating according to claim 1, characterized in that, after the multi-walled carbon-oriented carbon nanotube bundles, alkali, solvent, and tetraethyl orthosilicate are mixed and reacted, a silane coupling agent is added to continue the reaction. , to obtain ACNTB-SiO ₂ -coupling agent.
3. The durable super-hydrophobic composite material coating according to claim 2, wherein the weight ratio of the multi-wall carbon-oriented carbon nanotube bundle, tetraethyl orthosilicate, silane coupling agent, alkali, and solvent is (1~2 ): (9~14): (2~5): (9~12): (100~200).
4. The durable super-hydrophobic composite material coating of claim 2, wherein the multi-wall carbon-oriented carbon nanotube bundles have a diameter of 10-25 μm and a length of 30-100 μm; the silane coupling agent is γ-methacryloyl Oxypropyltrimethoxysilane, hexamethylsilazane, dodecyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane or hexadecyltrimethoxysilane; the base is Ammonia or triethanolamine; the solvent is water, ethanol, ethyl acetate or a mixture thereof.
5. The durable super-hydrophobic composite material coating according to claim 1, characterized in that, in the mixture, ACNTB-SiO ₂ -coupling agent, epoxy resin, diglycidyl ether-terminated polydimethylsiloxane, end- The weight parts of the amino hyperbranched polysiloxane are respectively 0-1 part, 70-100 parts, 0-70 parts and 30-60 parts; in the ACNTB-SiO ₂ -coupling agent suspension, the ACNTB-SiO ₂ -coupled The weight part of the joint agent is 4.0-20 parts.
6. The durable super-hydrophobic composite material coating according to claim 1, wherein the epoxy resin is bisphenol A epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A epoxy resin type epoxy resin, phenolic epoxy resin, multifunctional glycidyl ether resin, glycidyl ester type epoxy resin, halogen epoxy resin, one or more; diglycidyl ether-terminated polydimethylsiloxane The viscosity of the alkane is 50-10000 mPa.s/25°C, the specific gravity is 1.05-1.10/25°C; the amine value of the amino-terminated hyperbranched polysiloxane is 0.5-0.65 mol/100g.
7. The preparation method of the durable super-hydrophobic composite coating of claim 1, characterized in that it comprises the following steps: coating the ACNTB-SiO ₂ -coupling agent suspension on the ACNTB-SiO ₂ -coupling agent, epoxy resin, diglycidyl ether-terminated polydimethylsiloxane, and amino-terminated hyperbranched polysiloxane mixture on the gel surface, followed by curing to obtain a durable superhydrophobic composite coating; or ACNTB-SiO ₂ -Coupling agent suspension is coated on the gel surface of epoxy resin, amino-terminated hyperbranched polysiloxane mixture, and then cured to obtain durable superhydrophobic composite coating; or ACNTB-SiO ₂ -coupling The agent suspension is coated on the surface of the gel of epoxy resin, diglycidyl ether-terminated polydimethylsiloxane, and amino-terminated hyperbranched polysiloxane mixture, and then cured to obtain a durable superhydrophobic composite coating. layer; or coating the ACNTB-SiO ₂ -coupling agent suspension on the surface of the gel of ACNTB-SiO ₂ -coupling agent, epoxy resin, amino-terminated hyperbranched polysiloxane mixture, and then curing to obtain durable Type superhydrophobic composite coating.
8. The method for preparing a durable super-hydrophobic composite coating according to claim 7, wherein the curing process is (50~70°C)/1h+(80~150°C)/1-2h.
9. The application of the durable super-hydrophobic composite material coating of claim 1 in the preparation of a wear-resistant hydrophobic coating.
10. The application according to claim 9, wherein the wear-resistant hydrophobic coating has a multi-level micro/nano structured surface.