Preparation method of high-stability super-hydrophobic composite material of flexible armor structure for metal corrosion prevention

Abstract

The invention belongs to the technical field of corrosion prevention of metal materials in the marine environment, and particularly relates to a preparation method of a high-stability super-hydrophobic composite material of a flexible armor structure for metal corrosion prevention in the marine environment. The super-hydrophobic suspension liquid prepared through a phase separation method is sprayed to the surface of the flexible armor structure, and the high-stability super-hydrophobic composite material for the metal anti-corrosion flexible armor structure is obtained after complete curing. Wherein the preparation of the flexible armor structure comprises the following steps: dispersing an adhesive in a diluent to obtain an adhesive diluent, spraying the adhesive diluent on the surface of a pretreated base material, then bonding flexible armor particles to the surface of the material, and curing to obtain the flexible armor structure. According to the high-stability super-hydrophobic composite material of the flexible armor structure for metal corrosion prevention in the marine environment, durability and corrosion resistance tests prove that a sample has high stability, durability and corrosion resistance on the surface of a base material.

Description

Technical Field

[0001] The present invention belongs to the field of anti - corrosion of super - hydrophobic metal materials in marine environments, and specifically relates to a preparation method of a highly stable super - hydrophobic composite material with a flexible armor structure for metal anti - corrosion in marine environments. Background Technique

[0002] The artificially designed and constructed bionic super - hydrophobic material is a functional material with non - wettability. As a new type of material, super - hydrophobic materials have application prospects in many fields due to their functions such as waterproofing and self - cleaning, especially in the anti - corrosion and self - cleaning applications of metal materials. The metal corrosion problem in marine environments is extremely complex, such as the corrosion problems of offshore oil platforms, ships, and cross - sea bridges. This leads to waste of resources and even production safety problems. Currently, the problem of metal anti - corrosion in marine environments urgently needs to be solved. Therefore, new super - hydrophobic materials can provide important application references for metal material anti - corrosion.

[0003] In recent years, the artificial manufacture of super - hydrophobic materials has developed rapidly. However, in terms of the work reported so far, the improvement of the mechanical stability of super - hydrophobic anti - corrosion materials has always been an unsolved problem. Because the micro - nano rough structure and low - surface - energy super - hydrophobic nanoparticles on the surface of super - hydrophobic materials are very sensitive to the influence of mechanical external forces, resulting in poor mechanical stability of super - hydrophobic anti - corrosion materials. Therefore, improving the surface mechanical stability of super - hydrophobic anti - corrosion materials is crucial for their practical applications. Summary of the Invention

[0004] Aiming at the problems such as insufficient mechanical stability of current super - hydrophobic anti - corrosion materials, the present invention proposes a preparation method of a highly stable super - hydrophobic composite material with a flexible armor structure for metal anti - corrosion, which can effectively improve the mechanical stability of the super - hydrophobic anti - corrosion coating and effectively address the above - mentioned problems existing in super - hydrophobic anti - corrosion materials.

[0005] To achieve the above - mentioned goals, the technical solution adopted by the present invention is as follows: A preparation method of a highly stable super - hydrophobic composite material with a flexible armor structure for metal anti - corrosion, spraying a super - hydrophobic suspension onto the surface of the flexible armor structure, and obtaining a highly stable super - hydrophobic composite material with a flexible armor structure for metal anti - corrosion after curing; Among them, the preparation of the flexible armor structure: Dilute an epoxy resin - based adhesive in an organic solvent to make an epoxy diluent, then use the spraying method to spray the epoxy diluent onto the surface of a pre - treated metal substrate to obtain an epoxy adhesive layer, and then uniformly bond flexible armor particles to the surface of the epoxy adhesive layer, and obtain a flexible armor structure after curing.

[0006] Specifically, it includes the following steps: S1. Preparation of superhydrophobic modified nanoparticles: Take hydrophilic nanoparticles and ultrasonically disperse them in an organic solvent. Then, add a low surface energy organosilane coupling agent under stirring conditions for superhydrophobic modification to obtain superhydrophobic modified nanoparticles; S2. Preparation of superhydrophobic suspension by phase separation method: Dissolve polyester completely in an organic solvent. Then, add the superhydrophobic modified nanoparticles under stirring conditions and stir until completely dispersed. After the superhydrophobic nanoparticles are completely dispersed, add a non-solvent to induce phase separation. After the phase separation is completed, a superhydrophobic suspension is prepared; S3. Preparation of flexible armor structure: Dilute an epoxy resin adhesive in an organic solvent to make an epoxy diluent. Then, use the spraying method to spray the epoxy diluent onto the surface of a pretreated metal substrate to obtain an epoxy adhesive layer. Subsequently, uniformly bond flexible armor particles to the surface of the epoxy adhesive layer, and after curing, a flexible armor structure is prepared; S4. Preparation of a highly stable superhydrophobic composite material of a flexible armor structure for metal corrosion protection: Take the superhydrophobic suspension prepared in S2 and spray it onto the surface of the flexible armor structure prepared in S3 using a spray gun. After complete curing, a highly stable superhydrophobic composite material of a flexible armor structure for metal corrosion protection is prepared.

[0007] Further, in step S1, the nanoparticles are one or more of nano-aluminum oxide particles, nano-titanium dioxide particles, nano-silicon dioxide particles, and nano-zirconium dioxide particles; the low surface energy organosilane coupling agent is one or more of 1H,1H,2H,2H-perfluorodecyltrimethoxysilane, 1H,1H,2H,2H-perfluorooctyltrimethoxysilane, or 1H,1H,2H,2H-perfluorodecyltriethoxysilane.

[0008] Further, in step S1, the volume ratio of the low surface energy modifying reagent to the organic solvent is 0.05:3 to 0.15:3, and the mass concentration of the nanoparticles is 0.10 to 0.30 g / mL.

[0009] Further, in step S1, the reaction conditions for modification are to react at room temperature for 6 to 24 h, preferably at a temperature of 20 to 30 °C.

[0010] Further, in step S2, the polyester is one or more of polyurethane (PU), thermoplastic polyurethane (TPU), and Si-modified polyester (Si-PU); the organic solvents used are one or more of ethyl acetate, butyl acetate, and acetone; the mass concentration of the polyester is 0.01 to 0.10 g / mL.

[0011] Further, in step S2, the non-solvent required for non-solvent induced phase separation is absolute ethanol. Further, the volume ratio of the non-solvent to the organic solvent is 0.10 to 0.20 mL / mL.

[0012] Furthermore, the mass concentration of the superhydrophobic modified nanoparticles in step S2 is 0.01~0.10 g / mL.

[0013] Furthermore, the flexible armor particles in step S3 are recycled rubber particles from waste tires, with a particle size of 60~65 mesh. Further, the dosage of the flexible armor particles is 100~300 g / m 2 .

[0014] Furthermore, in step S3, the epoxy resin binder is a mixture of epoxy resin and curing agent in a mass ratio of 1:1, where the curing agent is polyamide (650), polyetheramine (D230), diethylenetriamine (DETA), or γ-aminopropyltriethoxysilane (KH-550).

[0015] Furthermore, in step S3, the mass fraction of the epoxy resin binder in the epoxy diluent is 20%~30%.

[0016] Furthermore, the substrate material in step S3 is carbon steel, copper sheet, titanium sheet, aluminum alloy, stainless steel, magnesium alloy, etc.

[0017] Furthermore, in step S4, the superhydrophobic suspension is sprayed onto the surface of the flexible armor structure by spraying method. Further, the dosage of the superhydrophobic suspension is 0.60~1.20 mL / cm 2 .

[0018] The advantages of the present invention compared with the prior art are as follows: 1. The high-stability superhydrophobic composite material of the flexible armor structure for metal corrosion prepared by the present invention, where the bottom layer is an epoxy adhesive material directly bonded to the pretreated substrate, which can effectively fix the flexible armor particles on the substrate surface. The middle layer is the flexible armor particle material, which can play a buffering role against external forces and protect the inner surface of the groove structure from being damaged by the superhydrophobic layer. The surface superhydrophobic material is a superhydrophobic layer obtained by spraying the superhydrophobic suspension prepared by the phase separation method, and its function is to provide superhydrophobicity.

[0019] 2. The highly stable superhydrophobic composite material with a flexible armor structure for metal anti-corrosion prepared by the present invention combines a superhydrophobic layer with a flexible armor structure, constructing a micro-nano hierarchical rough structure with ultra-high roughness and ultra-low surface free energy required for superhydrophobic coating materials; and the synergistic effect of the superhydrophobic layer and the flexible armor structure not only endows the composite material coating with excellent superhydrophobic properties but also effectively improves the mechanical stability and durability of the composite material coating. In the groove structure of the flexible armor structure, a superhydrophobic layer is prepared by spraying a superhydrophobic suspension. When the coating is affected by external forces, the flexible armor structure plays an effective protective role for the superhydrophobic layer, thereby reducing the degree of damage to the superhydrophobic layer caused by external forces, and effectively improving the superhydrophobic mechanical stability and durability of the composite material coating.

[0020] 3. The highly stable superhydrophobic composite material with a flexible armor structure for metal anti-corrosion prepared by the present invention has been tested for water contact angle and rolling angle, and all show good superhydrophobic properties. Moreover, the highly stable superhydrophobic composite material with a flexible armor structure for metal anti-corrosion prepared by the present invention can be applied to the surfaces of various metal substrates and shows good superhydrophobic properties.

[0021] 4. The highly stable superhydrophobic composite material with a flexible armor structure for metal anti-corrosion prepared by the present invention has been verified to have high stability through durability tests (including wear resistance tests of the coating under the condition of 100 g load with 2000-mesh sandpaper and tape peeling tests under 100 g load).

[0022] 5. The highly stable superhydrophobic composite material with a flexible armor structure for metal anti-corrosion prepared by the present invention has been verified to have good corrosion resistance on the surfaces of metal matrix materials through corrosion resistance tests (including electrochemical impedance spectroscopy (EIS) tests and exposure tests in a real marine atmospheric environment, etc.).

[0023] 6. The highly stable superhydrophobic composite material with a flexible armor structure for metal anti-corrosion prepared by the present invention has the advantages of simple preparation technology, easy operation, high efficiency, etc., and is of great significance for the application of superhydrophobic composite materials in actual production. Description of the Drawings

[0024] Figure 1 is a schematic structural diagram of the composite material coating prepared by the present invention; Figure 2 is an ordinary optical photograph of water droplets on the surface of the composite material coating of the sample prepared in Example 1 of the present invention and the contact angle and rolling angle diagram. Detailed Embodiments

[0025] The present invention will be described in detail below in conjunction with specific embodiments. The following embodiments will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be particularly pointed out that those of ordinary skill in the art can make changes and improvements without departing from the concept of the present invention. These all belong to the protection scope of the present invention.

[0026] The present invention constructs a flexible armor structure on the surface of a substrate by combining flexible rubber particles and a binder, which can effectively resist the damage of the rough structure on the surface of the superhydrophobic composite material caused by external forces, thereby improving the stability and durability of the superhydrophobic composite material coating, making the overall microstructure integrity and superhydrophobic performance of the coating more persistent. Through the synergistic effect of the superhydrophobic material and the flexible armor structure material, the composite material coating has good mechanical stability and superhydrophobic performance.

[0027] The preparation method of the high-stability superhydrophobic composite material with a flexible armor structure for metal corrosion prevention of the present invention is obtained by spraying a superhydrophobic surface layer suspension onto the surface of the flexible armor structure and completely curing it; Among them, the preparation of the flexible armor structure is as follows: Dilute the adhesive in an organic solvent to make a diluent, and then use the spraying method to spray the diluent onto the surface of the pretreated metal substrate to obtain an adhesive layer, and then uniformly bond the flexible armor particles to the surface of the adhesive layer, and cure to obtain the flexible armor structure.

[0028] Specifically, it includes the following steps: S1. Preparation of superhydrophobic modified nanoparticles: Take hydrophilic nanoparticles and ultrasonically disperse them in an organic solvent, and then add a low-surface-energy organosilane coupling agent under stirring conditions for superhydrophobic modification to obtain superhydrophobic modified nanoparticles; S2. Preparation of superhydrophobic suspension by phase separation method: Dissolve polyester completely in an organic solvent, then add the superhydrophobic modified nanoparticles under stirring conditions and stir until completely dispersed. After the superhydrophobic nanoparticles are completely dispersed, add a non-solvent to induce phase separation, and obtain a superhydrophobic suspension after the phase separation is completed; S3. Preparation of flexible armor structure: Dilute an epoxy resin adhesive in an organic solvent to make an epoxy diluent, and then use the spraying method to spray the epoxy diluent onto the surface of the pretreated metal substrate to obtain an epoxy adhesive layer, and then uniformly bond the flexible armor particles to the surface of the epoxy adhesive layer, and cure to obtain the flexible armor structure; S4. Preparation of high-stability superhydrophobic composite material with a flexible armor structure for metal corrosion prevention: Take the superhydrophobic suspension prepared in S2 and use a spray gun to spray it onto the surface of the flexible armor structure prepared in S3, and obtain a high-stability superhydrophobic composite material with a flexible armor structure for metal corrosion prevention after complete curing.

[0029] The pretreatment method of the metal substrate is as follows: The surface of the metal matrix material is polished with 800-mesh and 1500-mesh SiC sandpapers respectively, then immersed in ethanol for ultrasonic cleaning for 20 min, and then ultrasonic cleaned with deionized water 3 times, with each ultrasonic time of 10 min. After drying, it is reserved for use. For the convenience of comparison in the present invention, only the A5052 aluminum alloy metal matrix is used in Example 3, and the Q235 carbon steel metal matrix is used for preparation and testing in other cases. In actual situations, it can also be metal material matrices such as stainless steel, aluminum alloy, and magnesium alloy. Ethanol is used as the solvent in the examples and comparative examples, and in fact, it can also be one or several of ethanol, ethyl acetate, and butyl acetate. The present invention is not limited thereto. The solvents and raw materials used in the examples are all obtained commercially. Among them, the flexible armor particles are recycled rubber particles from waste tires, purchased from Chenqi Environmental Protection Raw Materials.

[0030] The specific implementation scheme is as follows: Example 1 S1. Preparation of superhydrophobic modified nanoparticles: Take 5.0 g of hydrophilic metal-based nano-aluminum oxide particles and disperse them in 30 mL of ethanol. After ultrasonic dispersion for 20 min, add 1.0 mL of 1H,1H,2H,2H-perfluorodecyltrimethoxysilane under magnetic stirring conditions. After continuous stirring reaction at room temperature for 12 h (this process is to perform superhydrophobic modification on the superhydrophilic metal-based nano-aluminum oxide particles through the hydrolysis and condensation reaction of fluorosilane), the obtained suspension is dried to obtain superhydrophobic nano-aluminum oxide particles.

[0031] S2. Preparation of superhydrophobic suspension by phase separation method: Take 0.2 g of thermoplastic polyurethane elastomer particles and completely dissolve them in 12 mL of ethyl acetate. Then add 0.25 g of superhydrophobic nano-aluminum oxide particles and stir magnetically for 3 h to uniformly disperse the superhydrophobic nano-aluminum oxide particles. Then add 2 mL of ethanol as a non-solvent to achieve non-solvent-induced TPU phase separation, stir magnetically for 15 min, and ultrasonic for 15 min. Finally, a uniform surface layer superhydrophobic suspension is successfully prepared.

[0032] S3. Preparation of flexible armor structure: Using absolute ethanol as a diluting solvent, a diluting solution of adhesive E44 and curing agent polyamide (the mass ratio of E44 to polyamide is 1:1) is prepared. Under a gas pressure of 0.3 MPa, the diluting solution is sprayed on the surface of the Q235 carbon steel substrate to prepare an adhesive layer. Then, 60 - 65-mesh recycled rubber particles from waste tires are uniformly bonded on the surface (the rubber particle dosage is 268 g / m 2 ) and a flexible armor structure is constructed after it is completely cured.

[0033] S4. Preparation of a highly stable superhydrophobic composite material for a flexible armor structure for metal corrosion prevention: Take the superhydrophobic suspension prepared in S2 and spray it onto the surface of the flexible armor structure prepared in S3 using a spray gun (spraying pressure is 0.3 MPa, spraying distance is 15 cm, and the suspension dosage is 1.0 mL / cm 2 ), and a highly stable superhydrophobic composite material for a flexible armor structure for metal corrosion prevention is obtained after complete curing.

[0034] Performance testing method for the prepared highly stable superhydrophobic composite material for a flexible armor structure for metal corrosion prevention (structural schematic diagram is shown in Figure 1 ): ① Wettability testing of the composite material coating: Use a contact angle measuring instrument to measure the contact angle and rolling angle of water droplets on the coating surface, so as to determine the superhydrophobic performance of the prepared coating. The dropped liquid droplets, contact angle, and rolling angle diagram are as shown in Figure 2 .

[0035] ② Mechanical stability testing of the composite material coating: (1) Sandpaper abrasion test: After the prepared coating sample is abraded under the conditions of 2000-mesh sandpaper and a 100 g load, use a contact angle measuring instrument to measure the contact angle and rolling angle of water droplets, so as to determine the superhydrophobic performance of the prepared coating after abrasion and evaluate its mechanical stability. (2) Tape peeling test: Stick 3M tape on the surface of the prepared coating sample, and after pressing and sticking tightly under a 100 g load and then quickly peeling it off, use a contact angle measuring instrument to measure the contact angle and rolling angle of water droplets, so as to determine the superhydrophobic performance of the prepared coating after abrasion and evaluate its mechanical stability.

[0036] ③ Corrosion resistance testing of the composite material coating - Electrochemical impedance spectroscopy testing: In a 3.5 wt.% NaCl aqueous solution system, adopt a three-electrode system, where the platinum plate electrode is the counter electrode, the Ag / AgCl electrode is the reference electrode, and the composite material coating with an exposed area of 1 cm 2 (the substrate is Q235 carbon steel) is the working electrode, and electrochemical impedance spectroscopy testing is carried out through an electrochemical workstation to determine the electrochemical performance of the prepared coating. Performance testing results of Example 1: 1. Wettability of the composite material coating: The contact angle and rolling angle of water droplets on the coating surface are measured using a contact angle measuring instrument. The water contact angle on the coating surface is 158.7 ± 1.1 °, and the rolling angle is 4.7 ± 0.1 ° (see Figure 2 ). Thus, it can be seen that the prepared highly stable superhydrophobic composite material for a flexible armor structure for metal corrosion prevention exhibits excellent superhydrophobic characteristics.

[0037] 2. Mechanical stability test of the composite material coating: (1) After the coating is worn 1200 times under the condition of 100 g load of 2000-mesh sandpaper, the water droplet contact angle is greater than 150 ° and the rolling angle is less than 10 °. Specifically: after 100 times of wear, the water contact angle of the coating is 155.3 ± 0.3 ° and the rolling angle is 5.0 ± 0.3 °; after 300 times of wear, the water contact angle of the coating is 154.4 ± 0.7 ° and the rolling angle is 5.7 ± 0.3 °; after 600 times of wear, the water contact angle of the coating is 154.0 ± 1.2 ° and the rolling angle is 5.6 ± 0.1 °; after 900 times of wear, the water contact angle of the coating is 153.9 ± 0.7 ° and the rolling angle is 5.3 ± 0.3 °; after 1200 times of wear, the water contact angle of the coating is 150.1 ± 0.6 ° and the rolling angle is 9.2 ± 0.4 °. It can be seen that the high-stability superhydrophobic composite material of the flexible armor structure for metal anti-corrosion prepared still shows good superhydrophobic characteristics to water droplets after 1200 times of sandpaper wear and has good mechanical wear resistance. (2) After the coating is peeled off 450 times with 3M tape, the water droplet contact angle is greater than 150 ° and the rolling angle is less than 10 °. Specifically: after 50 times of peeling, the water contact angle of the coating is 154.7 ± 0.3 ° and the rolling angle is 5.0 ± 0.2 °; after 100 times of peeling, the water contact angle of the coating is 153.6 ± 0.6 ° and the rolling angle is 5.0 ± 0.1 °; after 200 times of peeling, the water contact angle of the coating is 153.0 ± 0.6 ° and the rolling angle is 5.1 ± 0.2 °; after 300 times of peeling, the water contact angle of the coating is 152.4 ± 1.0 ° and the rolling angle is 6.8 ± 0.2 °; after 450 times of peeling, the water contact angle of the composite material coating is 150.0 ± 0.2 ° and the rolling angle is 9.4 ± 0.4 °. It can be seen that the high-stability superhydrophobic composite material of the flexible armor structure for metal anti-corrosion prepared still shows good superhydrophobic characteristics to water droplets after 450 times of 3M tape peeling and has good coating adhesion.

[0038] 3. Corrosion resistance test of the composite material coating - Electrochemical impedance spectroscopy test: The results show that the charge transfer resistance R ct = 9.53×10 10 Ω·cm 2 , compared with the blank Q235 carbon steel substrate (R ct = 1.18×10 3 Ω·cm 2 ), is increased by 7 orders of magnitude, showing good anti-corrosion and corrosion resistance performance.

[0039] Example 2 S1. Preparation of superhydrophobic modified nanoparticles: Take 5.0 g of superhydrophilic nano-titanium dioxide particles and disperse them in 30 mL of ethanol. After ultrasonic dispersion for 20 min, add 1.0 mL of 1H,1H,2H,2H-perfluorodecyltrimethoxysilane under magnetic stirring conditions and continuously stir and react at room temperature for 12 h (this process is to perform superhydrophobic modification on superhydrophilic nano-titanium dioxide particles through the hydrolysis and condensation reaction of fluorosilane). After drying the obtained suspension, superhydrophobic nano-titanium dioxide particles are prepared.

[0040] S2. Preparation of superhydrophobic suspension by phase separation method: Take 0.2 g of thermoplastic polyurethane elastomer particles and completely dissolve them in 12 mL of ethyl acetate. Then add 0.25 g of superhydrophobic nano-titanium dioxide particles and stir magnetically for 3 h to uniformly disperse the superhydrophobic nano-titanium dioxide particles. Then add 2 mL of ethanol as a non-solvent to achieve non-solvent-induced TPU phase separation, stir magnetically for 15 min, and ultrasonicate for 15 min. Finally, a uniform surface-layer superhydrophobic suspension is successfully prepared.

[0041] S3. Preparation of flexible armor structure: Using absolute ethanol as a diluting solvent, a dilution of adhesive E44 and curing agent polyamide (the mass ratio of E44 to polyamide is 1:1) is prepared. Under a gas pressure of 0.3 MPa, the dilution is sprayed on the surface of Q235 carbon steel substrate to prepare an adhesive layer. Then, 60 - 65 mesh waste tire recycled rubber particles are uniformly bonded on the surface (the amount of rubber particles used is 268 g / m 2 ) and a flexible armor structure is constructed after it is completely cured.

[0042] S4. Preparation of highly stable superhydrophobic composite material for flexible armor structure used in metal corrosion protection: Take the superhydrophobic suspension prepared in S2 and spray it onto the surface of the flexible armor structure prepared in S3 using a spray gun (spraying pressure is 0.3 MPa, spraying distance is 15 cm, and the amount of suspension used is 1.0 mL / cm 2 ). After complete curing, a highly stable superhydrophobic composite material for flexible armor structure used in metal corrosion protection is prepared.

[0043] The performance test method of the highly stable superhydrophobic composite material for flexible armor structure used in metal corrosion protection obtained in Example 2 is the same as that in Example 1, and the test results are as follows: 1. Wetting performance of the composite material coating: The contact angle and rolling angle of water droplets on the coating surface are measured using a contact angle measuring instrument. The water contact angle on the coating surface is 157.1 ° and the rolling angle is 4.3 °. It can be seen that the prepared highly stable superhydrophobic composite material for flexible armor structure used in metal corrosion protection exhibits excellent superhydrophobic characteristics.

[0044] 2. Mechanical stability test of the composite coating: (1) After the coating was worn 1200 times under a load of 100 g with 2000-mesh sandpaper, the water droplet contact angle was greater than 150 ° and the rolling angle was less than 10 °. It can be seen that the prepared high-stability superhydrophobic composite material for the flexible armor structure for metal anti-corrosion still exhibited good superhydrophobic properties towards water droplets after 1200 times of sandpaper wear, showing good mechanical abrasion resistance. (2) After the coating was peeled off 450 times with 3M tape, the water droplet contact angle was greater than 150 ° and the rolling angle was less than 10 °. It can be seen that the prepared high-stability superhydrophobic composite material for the flexible armor structure for metal anti-corrosion still exhibited good superhydrophobic properties towards water droplets after 450 times of 3M tape peeling, showing good coating adhesion.

[0045] 3. Corrosion resistance test of the composite coating - Electrochemical impedance spectroscopy test: The results showed that the charge transfer resistance R ct = 8.74×10 10 Ω cm 2 , compared with the blank Q235 carbon steel substrate (R ct = 1.18×10 3 Ω cm 2 ), was increased by 7 orders of magnitude, showing good anti-corrosion and corrosion resistance performance.

[0046] Example 3 S1. Preparation of superhydrophobic modified nanoparticles: Take 5.0 g of hydrophilic metal-based nano-aluminum oxide particles and disperse them in 30 mL of ethanol. After ultrasonic dispersion for 20 min, 1.0 mL of 1H,1H,2H,2H-perfluorooctyltrimethoxysilane was added under magnetic stirring conditions. After continuous stirring reaction at room temperature for 12 h (this process is to perform superhydrophobic modification on the superhydrophilic metal-based nano-aluminum oxide particles through the hydrolysis and condensation reaction of fluorosilane), the obtained suspension was dried to prepare superhydrophobic nano-aluminum oxide particles.

[0047] S2. Preparation of superhydrophobic suspension by phase separation method: Take 0.2 g of thermoplastic polyurethane elastomer particles and completely dissolve them in 12 mL of ethyl acetate. Then 0.25 g of superhydrophobic nano-aluminum oxide particles was added and magnetically stirred for 3 h to uniformly disperse the superhydrophobic nano-aluminum oxide particles. Then 2 mL of ethanol was added as a non-solvent to achieve non-solvent-induced TPU phase separation, magnetically stirred for 15 min, and ultrasonicated for 15 min. Finally, a uniform surface layer superhydrophobic suspension was successfully prepared.

[0048] S3. Preparation of the flexible armor structure: Using absolute ethanol as the diluting solvent, a dilution of adhesive E44 and curing agent polyamide (mass ratio of E44 to polyamide is 1:1) was prepared. Under a gas pressure of 0.3 MPa, the dilution was sprayed onto the surface of the Q235 carbon steel substrate to prepare the adhesive layer. Then, 60 - 65 mesh waste tire recycled rubber particles were evenly bonded to the surface (the amount of rubber particles used is 268 g / m 2 ), and after it was completely cured, the flexible armor structure was constructed.

[0049] S4. Preparation of the highly stable superhydrophobic composite material of the flexible armor structure for metal corrosion prevention: The superhydrophobic suspension prepared in S2 was taken and sprayed onto the surface of the flexible armor structure prepared in S3 using a spray gun (spraying pressure is 0.3 MPa, spraying distance is 15 cm, and the amount of suspension used is 1.0 mL / cm 2 ), and after it was completely cured, the highly stable superhydrophobic composite material of the flexible armor structure for metal corrosion prevention was obtained.

[0050] The performance test method of the highly stable superhydrophobic composite material of the flexible armor structure for metal corrosion prevention obtained in Example 3 is the same as that in Example 1, and the test results are as follows: 1. Wettability of the coating: The contact angle and rolling angle of water droplets on the coating surface were measured using a contact angle measuring instrument. The water contact angle on the coating surface was 156.6 °, and the rolling angle was 5.1 °. It can be seen that the highly stable superhydrophobic composite material of the flexible armor structure for metal corrosion prevention prepared shows excellent superhydrophobic properties.

[0051] 2. Mechanical stability test of the coating: (1) After the coating was worn 1200 times under the condition of a 100 g load of 2000 - mesh sandpaper, the water droplet contact angle was greater than 150 °, and the rolling angle was less than 10 °. It can be seen that the highly stable superhydrophobic composite material of the flexible armor structure for metal corrosion prevention still shows good superhydrophobic properties for water droplets after 1200 - time sandpaper wear and has good mechanical abrasion resistance. (2) After the coating was peeled 450 times with 3M tape, the water droplet contact angle was greater than 150 °, and the rolling angle was less than 10 °. It can be seen that the highly stable superhydrophobic composite material of the flexible armor structure for metal corrosion prevention still shows good superhydrophobic properties for water droplets after 450 - time 3M tape peeling and has good coating adhesion.

[0052] 3. Corrosion resistance test of the coating - Electrochemical impedance spectroscopy test: The results show that the charge transfer resistance R ct = 9.62×10 9 Ω·cm 2 , compared with the Q235 carbon steel substrate (R ct = 1.18×10 3 Ω·cm2 It has increased by six orders of magnitude, showing good anti-corrosion performance.

[0053] Example 4 S1. Preparation of superhydrophobic modified nanoparticles: Take 5.0 g of hydrophilic metal-based nano-aluminum oxide particles and disperse them in 30 mL of ethanol. After ultrasonic dispersion for 20 min, add 1.0 mL of 1H,1H,2H,2H-perfluorodecyltrimethoxysilane under magnetic stirring conditions. After continuous stirring reaction at room temperature for 12 h (this process is to superhydrophobically modify the superhydrophilic metal-based nano-aluminum oxide particles through the hydrolysis and condensation reaction of fluorosilane), the obtained suspension is dried to obtain superhydrophobic nano-aluminum oxide particles.

[0054] S2. Preparation of superhydrophobic suspension by phase separation method: Take 0.2 g of thermoplastic polyurethane elastomer particles and completely dissolve them in 12 mL of ethyl acetate. Then add 0.25 g of superhydrophobic nano-aluminum oxide particles and stir magnetically for 3 h to uniformly disperse the superhydrophobic nano-aluminum oxide particles. Then add 2 mL of ethanol as a non-solvent to achieve non-solvent-induced TPU phase separation, stir magnetically for 15 min, and sonicate for 15 min. Finally, a uniform surface layer superhydrophobic suspension is successfully prepared.

[0055] S3. Preparation of flexible armor structure: Using absolute ethanol as a diluting solvent, a diluting solution of adhesive E44 and curing agent polyamide (the mass ratio of E44 to polyamide is 1:1) is prepared. Under a gas pressure of 0.3 MPa, the diluting solution is sprayed on the surface of A5083 aluminum alloy substrate to prepare an adhesive layer. Then, 60 - 65 mesh waste tire recycled rubber particles are uniformly bonded on the surface (the rubber particle dosage is 268 g / m 2 ), and after it is completely cured, a flexible armor structure is constructed.

[0056] S4. Preparation of highly stable superhydrophobic composite material for flexible armor structure used in metal anti-corrosion: Take the superhydrophobic suspension prepared in S2 and spray it onto the surface of the flexible armor structure prepared in S3 using a spray gun (spraying pressure is 0.3 MPa, spraying distance is 15 cm, and the suspension dosage is 1.0 mL / cm 2 ), and after it is completely cured, a highly stable superhydrophobic composite material for flexible armor structure used in metal anti-corrosion is obtained.

[0057] The performance test method of the highly stable superhydrophobic composite material for flexible armor structure used in metal anti-corrosion obtained in Example 4 is the same as that in Example 1, and the test results are: 1. Coating wetting performance: The contact angle and rolling angle of water droplets on the coating surface were measured using a contact angle measuring instrument. The water contact angle on the coating surface was 158.2 °, and the rolling angle was 4.6 °. It can be seen that the prepared high-stability superhydrophobic composite material with a flexible armor structure for metal anti-corrosion exhibits excellent superhydrophobic properties.

[0058] 2. Coating mechanical stability test: (1) After the coating was worn 1200 times under a load of 100 g with 2000-mesh sandpaper, the water droplet contact angle was greater than 150 °, and the rolling angle was less than 10 °. It can be seen that the prepared high-stability superhydrophobic composite material with a flexible armor structure for metal anti-corrosion still exhibits good superhydrophobic properties for water droplets after 1200 times of sandpaper wear and has good mechanical wear resistance. (2) After the coating was peeled 450 times with 3M tape, the water droplet contact angle was greater than 150 °, and the rolling angle was less than 10 °. It can be seen that the prepared high-stability superhydrophobic composite material with a flexible armor structure for metal anti-corrosion still exhibits good superhydrophobic properties for water droplets after 450 times of 3M tape peeling and has good coating adhesion.

[0059] 3. Coating corrosion resistance test - Electrochemical impedance spectroscopy test: The results show that the charge transfer resistance R ct = 1.21×10 11 Ω·cm 2 , compared with the blank A5083 aluminum alloy substrate (R ct = 1.25×10 4 Ω·cm 2 ), it has increased by 7 orders of magnitude, showing good anti-corrosion and corrosion resistance performance.

[0060] Example 5 S1. Preparation of superhydrophobic modified nanoparticles: Take 5.0 g of hydrophilic metal-based nano-aluminum oxide particles and disperse them in 30 mL of ethanol. After ultrasonic dispersion for 20 min, add 1.0 mL of 1H,1H,2H,2H-perfluorodecyltrimethoxysilane under magnetic stirring conditions. After continuous stirring and reacting at room temperature for 12 h (this process is to perform superhydrophobic modification on the superhydrophilic metal-based nano-aluminum oxide particles through the hydrolysis and condensation reaction of fluorosilane), the obtained suspension was dried to obtain superhydrophobic nano-aluminum oxide particles.

[0061] S2. Preparation of superhydrophobic suspension by phase separation method: Take 0.2 g of Si-modified polyurethane (Si-PU) and completely dissolve it in 12 mL of ethyl acetate. Then add 0.25 g of superhydrophobic nano-aluminum oxide particles and stir magnetically for 3 h to uniformly disperse the superhydrophobic nano-aluminum oxide particles. Then add 2 mL of ethanol as a non-solvent to achieve non-solvent-induced phase separation of TPU, stir magnetically for 15 min, and sonicate for 15 min. Finally, a uniform surface-layer superhydrophobic suspension is successfully prepared.

[0062] S3. Preparation of flexible armor structure: Using absolute ethanol as a diluting solvent, a dilution of adhesive E44 and curing agent polyamide (mass ratio of E44 to polyamide is 1:1) is prepared. At a gas pressure of 0.3 MPa, the dilution is sprayed on the surface of Q235 carbon steel substrate to prepare an adhesive layer. Then, 60-65 mesh waste tire recycled rubber particles are uniformly bonded on the surface (rubber particle dosage is 268 g / m 2 ), and a flexible armor structure is constructed after it is completely cured.

[0063] S4. Preparation of highly stable superhydrophobic composite material for flexible armor structure used in metal corrosion prevention: Take the superhydrophobic suspension prepared in S2 and spray it onto the surface of the flexible armor structure prepared in S3 using a spray gun (spraying pressure is 0.3 MPa, spraying distance is 15 cm, suspension dosage is 1.0 mL / cm 2 ), and a highly stable superhydrophobic composite material for flexible armor structure used in metal corrosion prevention is obtained after it is completely cured.

[0064] The performance test method of the highly stable superhydrophobic composite material for flexible armor structure used in metal corrosion prevention obtained in Example 5 is the same as that in Example 1, and the test results are as follows: 1. Coating wetting performance: The contact angle and rolling angle of water droplets on the coating surface are measured using a contact angle measuring instrument. The water contact angle on the coating surface is 157.8 °, and the rolling angle is 4.8 °. It can be seen that the prepared highly stable superhydrophobic composite material for flexible armor structure used in metal corrosion prevention exhibits excellent superhydrophobic characteristics.

[0065] 2. Coating mechanical stability test: (1) After the coating is worn 1200 times under the condition of a 100 g load of 2000-mesh sandpaper, the water droplet contact angle is greater than 150 ° and the rolling angle is less than 10 °. It can be seen that the prepared high-stability superhydrophobic composite material with a flexible armor structure for metal anti-corrosion still exhibits good superhydrophobic properties towards water droplets after 1200 times of sandpaper wear, and has good mechanical abrasion resistance. (2) After the coating is peeled off with 3M tape 450 times, the water droplet contact angle is greater than 150 ° and the rolling angle is less than 10 °. It can be seen that the prepared high-stability superhydrophobic composite material with a flexible armor structure for metal anti-corrosion still exhibits good superhydrophobic properties towards water droplets after 450 times of 3M tape peeling, and has good coating adhesion.

[0066] 3. Coating corrosion resistance test - Electrochemical impedance spectroscopy test: The results show that the charge transfer resistance R ct = 8.23×10 10 Ω cm 2 , compared with the blank Q235 carbon steel substrate (R ct = 1.18×10 3 Ω cm 2 ), it has increased by 7 orders of magnitude, showing good anti-corrosion and corrosion resistance performance.

[0067] Example 6 S1. Preparation of superhydrophobic modified nanoparticles: Take 15.0 g of hydrophilic metal-based nano-aluminum oxide particles and disperse them in 100 mL of ethanol. After ultrasonic dispersion for 20 min, add 5.0 mL of 1H,1H,2H,2H-perfluorodecyltrimethoxysilane under magnetic stirring conditions. After continuous stirring reaction at room temperature for 12 h (this process is to perform superhydrophobic modification on the superhydrophilic metal-based nano-aluminum oxide particles through the hydrolysis and condensation reaction of fluorosilane), the obtained suspension is dried to prepare superhydrophobic nano-aluminum oxide particles.

[0068] S2. Preparation of superhydrophobic suspension by phase separation method: Take 0.2 g of thermoplastic polyurethane elastomer particles and completely dissolve them in 12 mL of ethyl acetate. Then add 0.25 g of superhydrophobic nano-aluminum oxide particles and stir magnetically for 3 h to uniformly disperse the superhydrophobic nano-aluminum oxide particles. Then add 2 mL of ethanol as a non-solvent to achieve non-solvent-induced TPU phase separation, stir magnetically for 15 min, and ultrasonically for 15 min. Finally, a uniform surface layer superhydrophobic suspension is successfully prepared.

[0069] S3. Preparation of the flexible armor structure: Using absolute ethanol as a diluting solvent, a dilution of adhesive E44 and curing agent polyamide (mass ratio of E44 to polyamide is 1:1) was prepared. Under a gas pressure of 0.3 MPa, the dilution was sprayed onto the surface of the Q235 carbon steel substrate to prepare an adhesive layer. Then, 60-65 mesh waste tire recycled rubber particles were evenly bonded to the surface (rubber particle dosage: 268 g / m 2 ), and after it was completely cured, the flexible armor structure was constructed.

[0070] S4. Preparation of the highly stable superhydrophobic composite material for the flexible armor structure used for metal corrosion prevention: The superhydrophobic suspension prepared in S2 was taken and sprayed onto the surface of the flexible armor structure prepared in S3 using a spray gun (spraying pressure: 0.3 MPa, spraying distance: 15 cm, suspension dosage: 1.0 mL / cm 2 ), and after it was completely cured, the highly stable superhydrophobic composite material for the flexible armor structure used for metal corrosion prevention was obtained.

[0071] The performance test method of the highly stable superhydrophobic composite material for the flexible armor structure used for metal corrosion prevention obtained in Example 6 is the same as that in Example 1, and the test results are as follows: 1. Coating wetting performance: The contact angle and rolling angle of water droplets on the coating surface were measured using a contact angle measuring instrument. The water contact angle on the coating surface was 158.4°, and the rolling angle was 4.3°. It can be seen that the prepared highly stable superhydrophobic composite material for the flexible armor structure used for metal corrosion prevention exhibits excellent superhydrophobic characteristics.

[0072] 2. Coating mechanical stability test: (1) After the coating was worn 1200 times under a load of 100 g with 2000-mesh sandpaper, the water droplet contact angle was greater than 150°, and the rolling angle was less than 10°. It can be seen that the prepared highly stable superhydrophobic composite material for the flexible armor structure used for metal corrosion prevention still exhibits good superhydrophobic characteristics for water droplets after 1200 times of sandpaper wear and has good mechanical abrasion resistance. (2) After the coating was peeled 450 times with 3M tape, the water droplet contact angle was greater than 150°, and the rolling angle was less than 10°. It can be seen that the prepared highly stable superhydrophobic composite material for the flexible armor structure used for metal corrosion prevention still exhibits good superhydrophobic characteristics for water droplets after 450 times of 3M tape peeling and has good coating adhesion.

[0073] 3. Coating corrosion resistance test - Electrochemical impedance spectroscopy test: The results show that the charge transfer resistance R ct = 9.15×10 10 Ω·cm 2 , compared with the blank Q235 carbon steel substrate (R ct = 1.18×10 3 Ω·cm2 It has increased by seven orders of magnitude, showing good anti-corrosion performance.

[0074] Example 7 S1. Preparation of superhydrophobic modified nanoparticles: Take 5.0 g of hydrophilic metal-based nano-aluminum oxide particles and disperse them in 30 mL of ethanol. After ultrasonic dispersion for 20 min, add 1.0 mL of 1H,1H,2H,2H-perfluorodecyltrimethoxysilane under magnetic stirring conditions. After continuous stirring reaction at room temperature for 12 h (this process is to superhydrophobically modify the superhydrophilic metal-based nano-aluminum oxide particles through the hydrolysis and condensation reaction of fluorosilane), the obtained suspension is dried to obtain superhydrophobic nano-aluminum oxide particles.

[0075] S2. Preparation of superhydrophobic suspension by phase separation method: Take 0.2 g of thermoplastic polyurethane elastomer particles and completely dissolve them in 12 mL of ethyl acetate. Then add 0.25 g of superhydrophobic nano-aluminum oxide particles and stir magnetically for 3 h to uniformly disperse the superhydrophobic nano-aluminum oxide particles. Then add 1.5 mL of ethanol as a non-solvent to achieve non-solvent-induced TPU phase separation, stir magnetically for 15 min, and ultrasonically for 15 min. Finally, a uniform surface layer superhydrophobic suspension is successfully prepared.

[0076] S3. Preparation of flexible armor structure: Using absolute ethanol as a diluting solvent, a dilution of adhesive E44 and curing agent polyamide (the mass ratio of E44 to polyamide is 1:1) is prepared. Under a gas pressure of 0.3 MPa, the dilution is sprayed on the surface of Q235 carbon steel substrate to prepare an adhesive layer. Then, 60-65 mesh waste tire recycled rubber particles are uniformly bonded on the surface (the amount of rubber particles used is 268 g / m 2 ), and a flexible armor structure is constructed after it is completely cured.

[0077] S4. Preparation of highly stable superhydrophobic composite material for flexible armor structure used in metal anti-corrosion: Take the superhydrophobic suspension prepared in S2 and spray it onto the surface of the flexible armor structure prepared in S3 using a spray gun (spraying pressure is 0.3 MPa, spraying distance is 15 cm, and the amount of suspension used is 1.0 mL / cm 2 ), and a highly stable superhydrophobic composite material for flexible armor structure used in metal anti-corrosion is obtained after it is completely cured.

[0078] The performance test method of the highly stable superhydrophobic composite material for flexible armor structure used in metal anti-corrosion obtained in Example 7 is the same as that in Example 1, and the test results are as follows: 1. Coating wetting performance: The contact angle and rolling angle of water droplets on the coating surface were measured using a contact angle measuring instrument. The water contact angle on the coating surface was 156.5°, and the rolling angle was 5.3°. It can be seen that the prepared high-stability superhydrophobic composite material with a flexible armor structure for metal anti-corrosion exhibits excellent superhydrophobic properties.

[0079] 2. Coating mechanical stability test: (1) After the coating was worn 1200 times under a load of 100 g with 2000-mesh sandpaper, the water droplet contact angle was greater than 150°, and the rolling angle was less than 10°. It can be seen that the prepared high-stability superhydrophobic composite material with a flexible armor structure for metal anti-corrosion still exhibits good superhydrophobic properties for water droplets after 1200 times of sandpaper wear and has good mechanical wear resistance. (2) After the coating was peeled 450 times with 3M tape, the water droplet contact angle was greater than 150°, and the rolling angle was less than 10°. It can be seen that the prepared high-stability superhydrophobic composite material with a flexible armor structure for metal anti-corrosion still exhibits good superhydrophobic properties for water droplets after 450 times of 3M tape peeling and has good coating adhesion.

[0080] 3. Coating corrosion resistance test - Electrochemical impedance spectroscopy test: The results show that the charge transfer resistance R ct = 8.07×10 10 Ω·cm 2 , compared with the blank Q235 carbon steel substrate (R ct = 1.18×10 3 Ω·cm 2 ), it has increased by 7 orders of magnitude, showing good anti-corrosion and corrosion resistance performance.

[0081] Example 8 S1. Preparation of superhydrophobic modified nanoparticles: Take 5.0 g of hydrophilic metal-based nano-aluminum oxide particles and disperse them in 30 mL of ethanol. After ultrasonic dispersion for 20 min, add 1.0 mL of 1H,1H,2H,2H-perfluorodecyltrimethoxysilane under magnetic stirring conditions. After continuous stirring and reaction at room temperature for 12 h (this process is to perform superhydrophobic modification on superhydrophilic metal-based nano-aluminum oxide particles through the hydrolysis and condensation reaction of fluorosilane), the obtained suspension was dried to obtain superhydrophobic nano-aluminum oxide particles.

[0082] S2. Preparation of superhydrophobic suspension by phase separation method: Take 0.2 g of thermoplastic polyurethane elastomer particles and completely dissolve them in 12 mL of ethyl acetate. Then add 0.25 g of superhydrophobic nano-aluminum oxide particles and stir magnetically for 3 h to uniformly disperse the superhydrophobic nano-aluminum oxide particles. Then add 2.0 mL of ethanol as a non-solvent to achieve non-solvent-induced TPU phase separation, stir magnetically for 15 min, and sonicate for 15 min. Finally, a uniform surface layer superhydrophobic suspension is successfully prepared.

[0083] S3. Preparation of flexible armor structure: Using absolute ethanol as a diluting solvent, a dilution of adhesive E44 and curing agent polyetheramine (D230) (the mass ratio of E44 to polyetheramine is 1:1) was prepared. Under a gas pressure of 0.3 MPa, the dilution was sprayed on the surface of a Q235 carbon steel substrate to prepare an adhesive layer. Then, waste tire recycled rubber particles with a mesh size of 60 - 65 were uniformly bonded to the surface (the amount of rubber particles used is 268 g / m 2 ), and a flexible armor structure was constructed after it was completely cured.

[0084] S4. Preparation of highly stable superhydrophobic composite material for flexible armor structure used in metal corrosion prevention: Take the superhydrophobic suspension prepared in S2 and spray it onto the surface of the flexible armor structure prepared in S3 using a spray gun (spraying pressure is 0.3 MPa, spraying distance is 15 cm, and the amount of suspension used is 1.0 mL / cm 2 ), and a highly stable superhydrophobic composite material for flexible armor structure used in metal corrosion prevention is obtained after it is completely cured.

[0085] The performance test method of the highly stable superhydrophobic composite material for flexible armor structure used in metal corrosion prevention obtained in Example 7 is the same as that in Example 1, and the test results are as follows: 1. Coating wetting performance: The contact angle and rolling angle of water droplets on the coating surface were measured using a contact angle measuring instrument. The water contact angle on the coating surface was 157.1°, and the rolling angle was 4.9°. It can be seen that the prepared highly stable superhydrophobic composite material for flexible armor structure used in metal corrosion prevention exhibits excellent superhydrophobic properties.

[0086] 2. Coating mechanical stability test: (1) After the coating is worn 1200 times under the condition of 100 g load of 2000-mesh sandpaper, the water droplet contact angle is greater than 150 ° and the rolling angle is less than 10 °. It can be seen that the prepared high-stability superhydrophobic composite material with a flexible armor structure for metal anti-corrosion still exhibits good superhydrophobic properties towards water droplets after 1200 times of sandpaper wear, and has good mechanical wear resistance. (2) After the coating is peeled 450 times with 3M tape, the water droplet contact angle is greater than 150 ° and the rolling angle is less than 10 °. It can be seen that the prepared high-stability superhydrophobic composite material with a flexible armor structure for metal anti-corrosion still exhibits good superhydrophobic properties towards water droplets after 450 times of 3M tape peeling, and has good coating adhesion.

[0087] 3. Coating corrosion resistance test - Electrochemical impedance spectroscopy test: The results show that the charge transfer resistance R ct = 9.11×10 10 Ω cm 2 , compared with the blank Q235 carbon steel substrate (R ct = 1.18×10 3 Ω cm 2 ), it is increased by 7 orders of magnitude, showing good anti-corrosion and corrosion resistance performance.

[0088] Comparative Example 1 1. Take 5.0 g of hydrophilic metal-based nano-aluminum oxide particles and disperse them in 30 mL of ethanol. After ultrasonic dispersion for 20 min, add 1.0 mL of 1H,1H,2H,2H-perfluorodecyltrimethoxysilane under magnetic stirring conditions. After continuous stirring and reacting at room temperature for 12 h (this process is to perform superhydrophobic modification on the superhydrophilic metal-based nano-aluminum oxide particles through the hydrolysis and condensation reaction of fluorosilane), the obtained suspension is dried to obtain superhydrophobic nano-aluminum oxide particles.

[0089] 2. Take 0.2 g of thermoplastic polyurethane elastomer particles and completely dissolve them in 12 mL of ethyl acetate. Then add 0.25 g of superhydrophobic nano-aluminum oxide particles and stir magnetically for 3 h to uniformly disperse the superhydrophobic nano-aluminum oxide particles. Then add 2.0 mL of ethanol as a non-solvent to achieve non-solvent-induced TPU phase separation, stir magnetically for 15 min, and ultrasonic for 15 min. Finally, a uniform surface-layer superhydrophobic suspension is successfully prepared. The suspension is sprayed onto the surface of a Q235 carbon steel substrate to obtain a superhydrophobic coating with only a surface layer.

[0090] The performance test method of the comparative coating sample obtained in Comparative Example 1 is the same as that in Example 1, and the test results are as follows: 1. Coating wetting performance: A water droplet was dropped on the surface of the coating, and using a contact angle measuring instrument, the water contact angle on the coating surface was measured to be 159.3 °, and the rolling angle was 3.8 °. It can be seen that the prepared surface layer superhydrophobic coating itself has excellent superhydrophobic properties.

[0091] 2. Coating mechanical stability test: (1) After the coating was worn 85 times under the condition of 100 g load of 2000 - mesh sandpaper, the water droplet contact angle was less than 150 °, and the rolling angle was greater than 10 °. It can be seen that the prepared surface layer superhydrophobic coating loses its superhydrophobic properties after being worn with a certain intensity, and its resistance to mechanical wear is poor. (2) After the coating was peeled 40 times with 3M tape, the water droplet contact angle was less than 150 °, and the rolling angle was greater than 10 °. It can be seen that the prepared surface layer superhydrophobic coating loses its superhydrophobic properties after a certain amount of tape peeling, and the adhesion between the coating and the substrate is poor.

[0092] 3. Coating corrosion resistance test - Electrochemical impedance spectroscopy test: The results show that the charge transfer resistance R ct = 8.69×10 7 Ω cm 2 , compared with the highly stable superhydrophobic composite material (R ct = 9.53×10 10 Ω cm 2 ) for metal anti - corrosion in Example 1, it decreased by 3 orders of magnitude, the electrochemical performance weakened, and the anti - corrosion and corrosion resistance performance decreased significantly.

[0093] From the test results of Comparative Example 1, it can be seen that due to the absence of an epoxy bonding layer and a flexible armor structure, the mechanical wear resistance of the coating decreased significantly, and the corrosion resistance also decreased significantly. However, after introducing the epoxy bonding layer and the flexible armor structure in the present invention, the mechanical wear resistance and corrosion resistance of the composite material coating have been significantly improved.

[0094] Comparative Example 2 1. Take 5.0 g of hydrophilic metal - based nano - aluminum oxide particles and disperse them in 30 mL of ethanol. After ultrasonic dispersion for 20 min, add 1.0 mL of 1H,1H,2H,2H - perfluorodecyltrimethoxysilane under magnetic stirring conditions. After continuous stirring and reacting at room temperature for 12 h (this process is to perform superhydrophobic modification on the superhydrophilic metal - based nano - aluminum oxide particles through the hydrolysis and condensation reaction of fluorosilane), the obtained suspension was dried to prepare superhydrophobic nano - aluminum oxide particles.

[0095] 2. Take 0.2 g of thermoplastic polyurethane elastomer particles and completely dissolve them in 12 mL of ethyl acetate. Then add 0.25 g of superhydrophobic nano-aluminum oxide particles and stir magnetically for 3 h to uniformly disperse the superhydrophobic nano-aluminum oxide particles. Then add 2.0 mL of ethanol as a non-solvent to achieve non-solvent-induced TPU phase separation, stir magnetically for 15 min, and sonicate for 15 min. Finally, a uniform surface-layer superhydrophobic suspension was successfully prepared.

[0096] 3. Weigh epoxy resin and its curing agent polyamide (650) according to a weight ratio of 1:1 and dilute them in 20 mL of ethanol under magnetic stirring to make an epoxy diluent. Then use a spray gun to spray the above epoxy diluent onto the surface of the pretreated Q235 carbon steel substrate material. Subsequently, spray the surface-layer superhydrophobic suspension onto its surface to obtain a superhydrophobic coating with an epoxy bonding layer plus a superhydrophobic surface layer.

[0097] The performance test method for the comparative coating sample obtained in Comparative Example 2 is the same as that in Example 1, and the test results are as follows: 1. Coating wetting performance: Drop water on the coating surface and measure it with a contact angle measuring instrument. The water contact angle on the coating surface is 158.9 °, and the rolling angle is 4.0 °. It can be seen that the prepared coating has excellent superhydrophobic properties.

[0098] 2. Coating mechanical stability test: (1) After the coating is worn 130 times under the condition of a 100 g load of 2000-mesh sandpaper, the water droplet contact angle is less than 150 °, and the rolling angle is greater than 10 °. It can be seen that the prepared surface-layer superhydrophobic coating loses its superhydrophobic properties after being worn with a certain intensity and has poor mechanical wear resistance. (2) After the coating is peeled 60 times with 3M tape, the water droplet contact angle is less than 150 °, and the rolling angle is greater than 10 °. It can be seen that the prepared surface-layer superhydrophobic coating loses its superhydrophobic properties after being peeled with a certain amount of tape, and the adhesion between the coating and the substrate is poor.

[0099] 3. Coating corrosion resistance test - electrochemical impedance spectroscopy test: The results show that the charge transfer resistance R ct = 9.66×10 8 Ω cm 2 , compared with the highly stable superhydrophobic composite material with a flexible armor structure for metal corrosion protection in Example 1 (R ct = 9.53×10 10 Ω cm 2 ), it has decreased by two orders of magnitude, the electrochemical performance has weakened, and the corrosion protection performance has decreased significantly.

[0100] From the test results of Comparative Example 2, it can be seen that due to the absence of the flexible armor structure, the mechanical abrasion resistance of the coating is significantly reduced, and the corrosion resistance is significantly decreased. However, after introducing the flexible armor structure in the present invention, the mechanical abrasion resistance and corrosion resistance of the composite coating are significantly improved.

[0101] Comparative Example 3 1. Disperse 5.0 g of hydrophilic metal-based nano-aluminum oxide particles in 30 mL of ethanol. After ultrasonic dispersion for 20 min, add 1.0 mL of 1H,1H,2H,2H-perfluorodecyltrimethoxysilane under magnetic stirring conditions. After continuous stirring reaction at room temperature for 12 h (this process is to perform superhydrophobic modification on the superhydrophilic metal-based nano-aluminum oxide particles through the hydrolysis and condensation reaction of fluorosilane), dry the obtained suspension to prepare superhydrophobic nano-aluminum oxide particles.

[0102] 2. Take 0.2 g of thermoplastic polyurethane elastomer particles and completely dissolve them in 12 mL of ethyl acetate. Then add 0.05 g of superhydrophobic nano-aluminum oxide particles and stir magnetically for 3 h to uniformly disperse the superhydrophobic nano-aluminum oxide particles. Then add 2.0 mL of ethanol as a non-solvent to achieve non-solvent-induced TPU phase separation, stir magnetically for 15 min, and ultrasonically for 15 min. Finally, a uniform surface layer superhydrophobic suspension is successfully prepared.

[0103] 3. Using absolute ethanol as a diluting solvent, prepare a dilution of adhesive E44 and curing agent polyamide (the mass ratio of E44 to polyamide is 1:1). Spray the dilution on the surface of Q235 carbon steel substrate under a gas pressure of 0.3 MPa to prepare an adhesive layer. Then evenly bond 60-65 mesh waste tire recycled rubber particles on the surface (the amount of rubber particles used is 268 g / m 2 ) and construct a flexible armor structure after it is completely cured.

[0104] 4. Take the superhydrophobic suspension prepared in 2 and spray it onto the surface of the flexible armor structure prepared in 3 using a spray gun (spraying pressure is 0.3 MPa, spraying distance is 15 cm, and the amount of suspension used is 1.0 mL / cm 2 ) and obtain a control coating sample after it is completely cured.

[0105] The performance test method of the comparative coating sample obtained in Comparative Example 3 is the same as that in Example 1, and the test results are as follows: Coating wetting performance: Drop water on the surface of the coating and measure it with a contact angle measuring instrument. The water contact angle on the coating surface is 136.1 °, indicating that the prepared control coating sample does not have superhydrophobic characteristics.

[0106] From the test results of Comparative Example 3, it can be seen that the dosage of the hydrophobic modified nanoparticles has an obvious effect on the superhydrophobic performance of the coating. If the concentration is too low, the coating sample cannot achieve superhydrophobic performance.

[0107] Comparative Example 4 1. Disperse 5.0 g of hydrophilic metal-based nano-aluminum oxide particles in 30 mL of ethanol. After ultrasonic dispersion for 20 min, add 0.1 mL of 1H,1H,2H,2H-perfluorodecyltrimethoxysilane under magnetic stirring conditions. After continuous stirring and reacting at room temperature for 12 h (this process is to superhydrophobically modify the superhydrophilic metal-based nano-aluminum oxide particles through the hydrolysis and condensation reaction of fluorosilane), dry the obtained suspension to prepare superhydrophobic nano-aluminum oxide particles.

[0108] 2. Take 0.2 g of thermoplastic polyurethane elastomer particles and completely dissolve them in 12 mL of ethyl acetate. Then add 0.25 g of superhydrophobic nano-aluminum oxide particles and stir magnetically for 3 h to uniformly disperse the superhydrophobic nano-aluminum oxide particles. Then add 2.0 mL of ethanol as a non-solvent to achieve non-solvent-induced TPU phase separation, stir magnetically for 15 min, and ultrasonically for 15 min. Finally, a uniform surface layer superhydrophobic suspension is successfully prepared.

[0109] 3. Using absolute ethanol as a diluting solvent, prepare a diluent of adhesive E44 and curing agent polyamide (the mass ratio of E44 to polyamide is 1:1). Spray the diluent on the surface of Q235 carbon steel substrate under a gas pressure of 0.3 MPa to prepare an adhesive layer. Then evenly bond 60-65 mesh waste tire recycled rubber particles on the surface (the dosage of rubber particles is 268 g / m 2 ) and construct a flexible armor structure after it is completely cured.

[0110] 4. Take the superhydrophobic suspension prepared in 2 and spray it onto the surface of the flexible armor structure prepared in 3 using a spray gun (spraying pressure is 0.3 MPa, spraying distance is 15 cm, and the dosage of the suspension is 1.0 mL / cm 2 ) and obtain a control coating sample after it is completely cured.

[0111] The performance test method of the comparative coating sample obtained in Comparative Example 4 is the same as that in Example 1, and the test results are as follows: Coating wetting performance: Drop water on the surface of the coating and measure it with a contact angle measuring instrument. The water contact angle on the coating surface is 132.6 °, indicating that the prepared control coating sample does not have superhydrophobic characteristics.

[0112] From the test results of Comparative Example 4, it can be seen that the dosage of the hydrophobic modifier has an obvious effect on the superhydrophobic performance of the coating. If the dosage is too low, the coating sample cannot achieve superhydrophobic performance.

[0113] Comparative Example 5 1. Take 5.0 g of hydrophilic metal-based nano-aluminum trioxide particles and disperse them in 30 mL of ethanol. After ultrasonic dispersion for 20 min, add 1.0 mL of 1H,1H,2H,2H-perfluorodecyltrimethoxysilane under magnetic stirring conditions. After continuous stirring and reacting at room temperature for 1 h (this process is to perform superhydrophobic modification on the superhydrophilic metal-based nano-aluminum trioxide particles through the hydrolysis and condensation reaction of fluorosilane), dry the obtained suspension to prepare superhydrophobic nano-aluminum trioxide particles.

[0114] 2. Take 0.2 g of thermoplastic polyurethane elastomer particles and completely dissolve them in 12 mL of ethyl acetate. Then add 0.25 g of superhydrophobic nano-aluminum trioxide particles and stir magnetically for 3 h to uniformly disperse the superhydrophobic nano-aluminum trioxide particles. Then add 2.0 mL of ethanol as a non-solvent to achieve non-solvent-induced TPU phase separation, stir magnetically for 15 min, and ultrasonically for 15 min. Finally, a uniform surface-layer superhydrophobic suspension was successfully prepared.

[0115] 3. Using absolute ethanol as a diluting solvent, prepare a dilution of adhesive E44 and curing agent polyamide (the mass ratio of E44 to polyamide is 1:1). Spray the dilution on the surface of Q235 carbon steel substrate under a gas pressure of 0.3 MPa to prepare an adhesive layer. Then evenly bond 60 - 65 mesh waste tire recycled rubber particles on the surface (the amount of rubber particles used is 268 g / m 2 ) and construct a flexible armor structure after it is completely cured.

[0116] 4. Take the superhydrophobic suspension prepared in 2 and spray it onto the surface of the flexible armor structure prepared in 3 using a spray gun (spraying pressure is 0.3 MPa, spraying distance is 15 cm, and the amount of suspension used is 1.0 mL / cm 2 ). After complete curing, a control coating sample was prepared.

[0117] The performance test method of the comparative coating sample obtained in Comparative Example 5 is the same as that in Example 1, and the test results are as follows: Coating wetting performance: Drop water on the surface of the coating and measure it with a contact angle measuring instrument. The water contact angle on the coating surface is 141.3 °, indicating that the prepared control coating sample does not have superhydrophobic properties.

[0118] From the test results of Comparative Example 5, it can be seen that the reaction time of low surface energy modification has a great influence on the superhydrophobic modification of nanoparticles. Too short a time will cause the coating to not reach superhydrophobic performance.

[0119] Comparative Example 6 1. Take 5.0 g of hydrophilic metal-based nano-aluminum oxide particles and disperse them in 30 mL of ethanol. After ultrasonic dispersion for 20 min, add 1.0 mL of 1H,1H,2H,2H-perfluorodecyltrimethoxysilane under magnetic stirring conditions. After continuous stirring and reacting at room temperature for 12 h (this process is to perform superhydrophobic modification on the superhydrophilic metal-based nano-aluminum oxide particles through the hydrolysis and condensation reaction of fluorosilane), dry the obtained suspension to prepare superhydrophobic nano-aluminum oxide particles.

[0120] 2. Take 0.2 g of thermoplastic polyurethane elastomer particles and completely dissolve them in 12 mL of ethyl acetate. Then add 0.25 g of superhydrophobic nano-aluminum oxide particles and stir magnetically for 3 h to uniformly disperse the superhydrophobic nano-aluminum oxide particles. Then add 2.0 mL of ethanol as a non-solvent to achieve non-solvent-induced TPU phase separation, stir magnetically for 15 min, and ultrasonicate for 15 min. Finally, a uniform surface layer superhydrophobic suspension is successfully prepared.

[0121] 3. Using anhydrous ethanol as a diluting solvent, prepare a dilution of adhesive E44 and curing agent polyamide (the mass ratio of E44 to polyamide is 1:1). Spray the dilution on the surface of Q235 carbon steel substrate under a gas pressure of 0.3 MPa to prepare an adhesive layer. Then evenly bond 100 - 110 mesh waste tire recycled rubber particles on the surface (the amount of rubber particles used is 268 g / m 2 ) and construct a flexible armor structure after it is completely cured.

[0122] 4. Take the superhydrophobic suspension prepared in 2 and spray it onto the surface of the flexible armor structure prepared in 3 using a spray gun (spraying pressure is 0.3 MPa, spraying distance is 15 cm, and the amount of suspension used is 1.0 mL / cm 2 ) and obtain a control coating sample after it is completely cured.

[0123] The performance test method of the comparative coating sample obtained in Comparative Example 6 is the same as that in Example 1, and the test results are as follows: 1. Coating wetting performance: Drop water on the surface of the coating and measure it using a contact angle measuring instrument. The water contact angle on the coating surface is 156.7 °, and the rolling angle is 5.1 °. It can be seen that the prepared coating has excellent superhydrophobic properties.

[0124] 2. Coating mechanical stability test: (1) After the coating was worn 180 times under a load of 100 g with 2000-mesh sandpaper, the water droplet contact angle was less than 150 ° and the rolling angle was greater than 10 °. It can be seen that the prepared surface superhydrophobic coating lost its superhydrophobic property after being worn with a certain intensity, indicating poor mechanical wear resistance. (2) After the coating was peeled 85 times with 3M tape, the water droplet contact angle was less than 150 ° and the rolling angle was greater than 10 °. It can be seen that the prepared surface superhydrophobic coating lost its superhydrophobic property after a certain amount of tape peeling, indicating poor adhesion between the coating and the substrate.

[0125] 3. Coating corrosion resistance test - Electrochemical impedance spectroscopy test: The results show that the charge transfer resistance R ct = 6.92×10 9 Ω·cm 2 , which is one order of magnitude lower than that of the highly stable superhydrophobic composite material with a flexible armor structure for metal corrosion protection in Example 1 (R ct = 9.53×10 10 Ω·cm 2 ). The electrochemical performance weakens, and the anti-corrosion and corrosion resistance performance decreases significantly.

[0126] From the test results of Comparative Example 6, it can be seen that due to the too small size of the flexible armor structure, the mechanical wear resistance of the coating decreases significantly, and the corrosion resistance also decreases. However, in the present invention, after introducing a flexible armor structure with a suitable size, the mechanical wear resistance and corrosion resistance of the composite material coating are significantly improved.

[0127] Comparative Example 7 1. Take 5.0 g of hydrophilic metal-based nano-aluminum oxide particles and disperse them in 30 mL of ethanol. After ultrasonic dispersion for 20 min, add 1.0 mL of 1H,1H,2H,2H-perfluorodecyltrimethoxysilane under magnetic stirring conditions. After continuous stirring and reacting at room temperature for 12 h (this process is to perform superhydrophobic modification on the superhydrophilic metal-based nano-aluminum oxide particles through the hydrolysis and condensation reaction of fluorosilane), the obtained suspension was dried to prepare superhydrophobic nano-aluminum oxide particles.

[0128] 2. Take 0.2 g of thermoplastic polyurethane elastomer particles and completely dissolve them in 12 mL of ethyl acetate. Then add 0.25 g of superhydrophobic nano-aluminum oxide particles and stir magnetically for 3 h to uniformly disperse the superhydrophobic nano-aluminum oxide particles. Then add 2.0 mL of ethanol as a non-solvent to achieve non-solvent-induced TPU phase separation, stir magnetically for 15 min, and ultrasonically for 15 min. Finally, a uniform surface superhydrophobic suspension was successfully prepared.

[0129] 3. Using absolute ethanol as the diluting solvent, a diluting solution of adhesive E44 and curing agent polyamide (the mass ratio of E44 to polyamide is 1:1) was prepared. Under a gas pressure of 0.3 MPa, the diluting solution was sprayed onto the surface of Q235 carbon steel substrate to prepare an adhesive layer. Then, waste tire recycled rubber particles with a mesh size of 40 - 50 were evenly bonded to the surface (the amount of rubber particles used is 268 g / m 2 ), and a flexible armor structure was constructed after it was completely cured.

[0130] 4. The superhydrophobic suspension prepared in 2 was taken and sprayed onto the surface of the flexible armor structure prepared in 3 using a spray gun (the spraying pressure is 0.3 MPa, the spraying distance is 15 cm, and the amount of suspension used is 1.0 mL / cm 2 ), and a control coating sample was obtained after it was completely cured.

[0131] The performance of the comparative coating sample obtained in Comparative Example 7 was tested in the same way as in Example 1, and the test results are as follows: 1. Coating wetting performance: A water droplet was dropped on the coating surface, and it was measured with a contact angle measuring instrument that the water contact angle on the coating surface was 156.7 ° and the rolling angle was 5.1 °. It can be seen that the prepared coating has excellent superhydrophobic properties.

[0132] 2. Coating mechanical stability test: (1) After the coating was worn 120 times under the condition of a 100 g load of 2000 - mesh sandpaper, the water droplet contact angle was less than 150 ° and the rolling angle was greater than 10 °. It can be seen that the prepared surface superhydrophobic coating loses its superhydrophobic properties after being worn with a certain intensity and has poor mechanical wear resistance. (2) After the coating was peeled 65 times with 3M tape, the water droplet contact angle was less than 150 ° and the rolling angle was greater than 10 °. It can be seen that the prepared surface superhydrophobic coating loses its superhydrophobic properties after being peeled with a certain amount of tape, and the adhesion between the coating and the substrate is poor.

[0133] 3. Coating corrosion resistance test - electrochemical impedance spectroscopy test: The results show that the charge transfer resistance R ct = 4.85×10 9 Ω cm 2 , compared with the highly stable superhydrophobic composite material of the flexible armor structure for metal corrosion protection in Example 1 (R ct = 9.53×10 10 Ω cm 2 ), it decreased by one order of magnitude, the electrochemical performance weakened, and the anti - corrosion and corrosion resistance performance decreased significantly.

[0134] From the test results of Comparative Example 7, it can be seen that due to the too large size of the flexible armor structure, the mechanical wear resistance of the coating is significantly reduced, and the corrosion resistance also decreases. However, after introducing a flexible armor structure with a suitable size in the present invention, the mechanical wear resistance and corrosion resistance of the composite coating are significantly improved.

[0135] Comparative Example 8 1. Take 5.0 g of hydrophilic metal-based nano-aluminum trioxide particles and disperse them in 30 mL of ethanol. After ultrasonic dispersion for 20 min, add 1.0 mL of 1H,1H,2H,2H-perfluorodecyltrimethoxysilane under magnetic stirring conditions. After continuous stirring reaction at room temperature for 12 h (this process is to perform superhydrophobic modification on the superhydrophilic metal-based nano-aluminum trioxide particles through the hydrolysis and condensation reaction of fluorosilane), dry the obtained suspension to obtain superhydrophobic nano-aluminum trioxide particles.

[0136] 2. Take 0.2 g of thermoplastic polyurethane elastomer particles and completely dissolve them in 12 mL of ethyl acetate. Then add 0.25 g of superhydrophobic nano-aluminum trioxide particles and stir magnetically for 3 h to uniformly disperse the superhydrophobic nano-aluminum trioxide particles. Then add 2.0 mL of ethanol as a non-solvent to achieve non-solvent-induced TPU phase separation, stir magnetically for 15 min, and ultrasonically for 15 min. Finally, a uniform surface layer superhydrophobic suspension is successfully prepared.

[0137] 3. Using absolute ethanol as a diluting solvent, prepare a dilution of adhesive E44 and curing agent polyamide (the mass ratio of E44 to polyamide is 1:1). Spray the dilution on the surface of Q235 carbon steel substrate under a gas pressure of 0.3 MPa to prepare an adhesive layer. Then evenly bond 60-65 mesh waste tire recycled rubber particles on the surface (the amount of rubber particles used is 268 g / m 2 ) and construct a flexible armor structure after it is completely cured.

[0138] 4. Take the superhydrophobic suspension prepared in 2 and spray it onto the surface of the flexible armor structure prepared in 3 using a spray gun (spraying pressure is 0.3 MPa, spraying distance is 15 cm, and the amount of suspension used is 0.1 mL / cm 2 ). After complete curing, a control coating sample is prepared.

[0139] The performance test method of the comparative coating sample obtained in Comparative Example 8 is the same as that in Example 1, and the test results are as follows: Coating wetting performance: Drop water on the coating surface and measure it with a contact angle measuring instrument. The water contact angle on the coating surface is 139.2 °, indicating that the prepared control coating sample does not have superhydrophobic properties.

[0140] It can be seen from the test results of Comparative Example 8 that the amount of the suspension used has a certain influence on the superhydrophobic performance of the coating. If the amount is too small, the coating cannot achieve superhydrophobic performance.

Claims

1. A method for preparing a highly stable super-hydrophobic composite material for a flexible armor structure for metal corrosion protection, characterized in that: The steps include: S1. Preparation of super-hydrophobic modified nanoparticles: ultrasonically dispersing hydrophilic nanoparticles in an organic solvent, and then adding a low surface energy organic silane coupling agent under stirring conditions to perform super-hydrophobic modification to obtain super-hydrophobic modified nanoparticles; S2. Preparation of super-hydrophobic suspension by phase separation method: taking polyester and completely dissolving it in an organic solvent, then adding super-hydrophobic modified nanoparticles under stirring and stirring until completely dispersed, adding non-solvent to induce phase separation after the super-hydrophobic nanoparticles are completely dispersed, and preparing super-hydrophobic suspension after phase separation is completed; S3, preparation of a flexible armor structure: taking an epoxy resin adhesive and diluting it in an organic solvent to prepare an epoxy diluent, and then spraying the epoxy diluent onto the surface of the pretreated metal substrate by a spraying method to prepare an epoxy adhesive layer, and then evenly bonding the flexible armor particles to the surface of the epoxy adhesive layer, and preparing a flexible armor structure after curing; S4. Preparation of highly stable super-hydrophobic composite materials for flexible armor structures for metal corrosion protection: Take the super-hydrophobic suspension prepared in S2 and spray it onto the surface of the flexible armor structure prepared in S3 using a spray gun. After it is completely cured, a highly stable super-hydrophobic composite material for a flexible armor structure for metal corrosion protection is obtained.

2. The method for preparing a highly stable super-hydrophobic composite material for a flexible armor structure for metal corrosion protection according to claim 1, wherein: In step S1, the nanoparticles are one or more of nano-aluminum oxide particles, nano-silicon dioxide particles, nano-titanium dioxide particles, and nano-zirconium dioxide particles; the low surface energy organic silane coupling agent is one or more of 1H, 1H, 2H, 2H-perfluorodecyltrimethoxysilane, 1H, 1H, 2H, 2H-perfluorooctyltrimethoxysilane or 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane.

3. The method for preparing a highly stable super-hydrophobic composite material for a flexible armor structure for metal corrosion protection according to claim 1, wherein: In the step S1, the volume ratio of the low surface energy organosilane coupling agent to the organic solvent is 0.05:3-0.15:3, and the mass concentration of the nanoparticles is 0.10-0.30 g / mL; the reaction conditions for the modification in S1 are room temperature, and the reaction time is 6-24 h.

4. The method for preparing a highly stable super-hydrophobic composite material for a flexible armor structure for metal corrosion protection according to claim 1, wherein: In step S2, the polyester is one or more of polyurethane, thermoplastic polyurethane and Si-modified polyester; the organic solvent is one or more of ethyl acetate, butyl acetate and acetone; and the mass concentration of the polyester is 0.01-0.10 g / mL.

5. The method for preparing a highly stable super-hydrophobic composite material for a flexible armor structure for metal corrosion protection according to claim 1, characterized in that: The non-solvent for non-solvent-induced phase separation in step S2 is anhydrous ethanol, and the volume ratio of the non-solvent to the organic solvent is 0.10-0.20 mL / mL.

6. The method for preparing a highly stable super-hydrophobic composite material for a flexible armor structure for metal corrosion protection according to claim 1, characterized in that: The mass concentration of the superhydrophobic modified nanoparticles in step S2 is 0.01-0.10 g / mL.

7. The method for preparing a highly stable super-hydrophobic composite material for a flexible armor structure for metal corrosion protection according to claim 1 or 5, characterized in that: In step S3, the flexible armor particles are recycled rubber particles from waste tires, with a particle size of 60-65 meshes, and the amount of the flexible armor particles is 100-300 g / m 2 .

8. The method for preparing a highly stable super-hydrophobic composite material for a flexible armor structure for metal corrosion protection according to claim 1, characterized in that: In step S3, the epoxy resin adhesive is a mixture of epoxy resin and curing agent in a mass ratio of 1:1, wherein the curing agent is polyamide, polyetheramine, diethylenetriamine or γ-aminopropyltriethoxysilane.

9. The method for preparing a highly stable super-hydrophobic composite material for a flexible armor structure for metal corrosion protection according to claim 1, characterized in that: The mass fraction of the epoxy resin binder in the epoxy diluent in step S3 is 20% to 30%.

10. The method for preparing a highly stable super-hydrophobic composite material for a flexible armor structure for metal corrosion protection according to claim 1, characterized in that: In step S4, the super hydrophobic suspension is sprayed onto the surface of the flexible armor structure by spraying, and the amount of the super hydrophobic suspension is 0.60-1.20 mL / cm 2 .

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