A method for preparing a highly stable superhydrophobic composite material with a flexible armor structure for metal corrosion protection

Abstract

This invention belongs to the field of metal corrosion protection technology in marine environments, specifically relating to a method for preparing a highly stable superhydrophobic composite material with a flexible armor structure for metal corrosion protection in marine environments. A superhydrophobic suspension prepared by phase separation is sprayed onto the surface of a flexible armor structure, and after complete curing, a highly stable superhydrophobic composite material for metal corrosion protection is obtained. The preparation of the flexible armor structure involves: dispersing an adhesive in a diluent to obtain an adhesive dilution; spraying the adhesive dilution onto a pre-treated substrate surface; then bonding flexible armor particles to the material surface; and finally curing to obtain the flexible armor structure. The highly stable superhydrophobic composite material with a flexible armor structure for metal corrosion protection in marine environments prepared by this invention has undergone durability and corrosion resistance tests, verifying that the sample possesses high stability, durability, and corrosion resistance on the substrate surface.

Description

Technical Field

[0001] This invention belongs to the field of corrosion protection of superhydrophobic metal materials for marine environments, specifically relating to a method for preparing a highly stable superhydrophobic composite material with a flexible armor structure for metal corrosion protection in marine environments. Background Technology

[0002] Artificially designed and constructed biomimetic superhydrophobic materials are functional materials with non-wetting properties. As a novel type of material, superhydrophobic materials have promising applications in many fields due to their waterproof and self-cleaning functions, especially in the corrosion protection and self-cleaning of metal materials. Metal corrosion in marine environments is extremely complex, as seen in offshore oil platforms, ships, and cross-sea bridges. This leads to resource waste and even production safety issues, making the problem of metal corrosion protection in marine environments an urgent issue to be addressed. Therefore, novel superhydrophobic materials can provide important application references for metal material corrosion protection.

[0003] In recent years, the artificial manufacturing of superhydrophobic materials has developed rapidly. However, based on current reported work, improving the mechanical stability of superhydrophobic anti-corrosion materials remains an unsolved problem. This is because the micro-nano rough structure of the superhydrophobic material surface and the low surface area of ​​the superhydrophobic nanoparticles are highly sensitive to the influence of external mechanical forces, resulting in poor mechanical stability. Therefore, improving the surface mechanical stability of superhydrophobic anti-corrosion materials is crucial for their practical applications. Summary of the Invention

[0004] To address the issues of insufficient mechanical stability in current superhydrophobic anticorrosive materials, this invention proposes a method for preparing a highly stable superhydrophobic composite material with a flexible armor structure for metal corrosion protection. This method can effectively improve the mechanical stability of superhydrophobic anticorrosive coatings and effectively solve the above-mentioned problems of superhydrophobic anticorrosive materials.

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

[0006] A method for preparing a highly stable superhydrophobic composite material with a flexible armor structure for metal corrosion protection involves spraying a superhydrophobic suspension onto the surface of a flexible armor structure and curing it to obtain the highly stable superhydrophobic composite material with a flexible armor structure for metal corrosion protection.

[0007] The preparation of the flexible armor structure involves diluting an epoxy resin adhesive in an organic solvent to prepare an epoxy diluent, then spraying the epoxy diluent onto the surface of a pre-treated metal substrate to obtain an epoxy adhesive layer. Subsequently, flexible armor particles are uniformly bonded to the surface of the epoxy adhesive layer, and after curing, a flexible armor structure is obtained.

[0008] Specifically, the steps include the following:

[0009] S1. Preparation of superhydrophobic modified nanoparticles: Hydrophilic nanoparticles were ultrasonically dispersed in an organic solvent, and then a low surface energy organosilane coupling agent was added under stirring conditions to obtain superhydrophobic modified nanoparticles.

[0010] S2. Preparation of superhydrophobic suspension by phase separation method: Polyester is completely dissolved in an organic solvent, and then superhydrophobic modified nanoparticles are added under stirring and stirred until completely dispersed. After the superhydrophobic nanoparticles are completely dispersed, a non-solvent is added to induce phase separation. After phase separation is completed, a superhydrophobic suspension is obtained.

[0011] S3. Preparation of flexible armor structure: Epoxy resin adhesive is diluted in an organic solvent to prepare epoxy diluent. Then, the epoxy diluent is sprayed onto the surface of the pretreated metal substrate to obtain an epoxy adhesive layer. Flexible armor particles are then uniformly bonded to the surface of the epoxy adhesive layer and cured to obtain a flexible armor structure.

[0012] S4. Preparation of a highly stable superhydrophobic composite material with a flexible armor structure for metal corrosion protection: The superhydrophobic suspension prepared in S2 is sprayed onto the surface of the flexible armor structure prepared in S3 using a spray gun. After complete curing, a highly stable superhydrophobic composite material with a flexible armor structure for metal corrosion protection is obtained.

[0013] Further, in step S1, the nanoparticles are one or more of nano-alumina particles, nano-titanium dioxide particles, nano-silica 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.

[0014] Furthermore, in step S1, the volume ratio of the low surface energy modifying agent 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.

[0015] Furthermore, the modification reaction conditions in step S1 are 6-24 h at room temperature, preferably 20-30℃.

[0016] Further, in step S2, the polyester is one or more of polyurethane (PU), thermoplastic polyurethane (TPU), and Si-modified polyester (Si-PU); the organic solvent used 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.

[0017] Furthermore, the non-solvent required for non-solvent-induced phase separation in step S2 is anhydrous ethanol, and even further, the volume ratio of the non-solvent to the organic solvent is 0.10~0.20 mL / mL.

[0018] Furthermore, in step S2, the mass concentration of the superhydrophobic modified nanoparticles is 0.01~0.10 g / mL.

[0019] Furthermore, in step S3, the flexible armor particles are recycled rubber particles from waste tires with a particle size of 60-65 mesh. Even further, the dosage of the flexible armor particles is 100-300 g / m³. 2 .

[0020] Further, 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 (650), polyetheramine (D230), diethylenetriamine (DETA), or γ-aminopropyltriethoxysilane (KH-550).

[0021] Furthermore, in step S3, the mass fraction of epoxy resin adhesive in the epoxy diluent is 20%~30%.

[0022] Furthermore, in step S3, the base material is carbon steel, copper sheet, titanium sheet, aluminum alloy, stainless steel, or magnesium alloy, etc.

[0023] Furthermore, in step S4, the superhydrophobic suspension is sprayed onto the surface of the flexible armor structure using a spraying method; even further, the amount of superhydrophobic suspension used is 0.60~1.20 mL / cm³. 2 .

[0024] The advantages of this invention compared to the prior art are as follows:

[0025] 1. The high-stability superhydrophobic composite material with flexible armor structure for metal corrosion protection prepared in this invention comprises an epoxy adhesive material directly bonded to a pretreated substrate, which can effectively fix the flexible armor particles to the substrate surface; a flexible armor particle material in the middle, which can buffer external forces and protect the superhydrophobic layer on the inner surface of the groove structure from damage; and a superhydrophobic layer on the surface, which is a superhydrophobic suspension prepared by phase separation method and obtained by spraying, which provides superhydrophobicity.

[0026] 2. The high-stability superhydrophobic composite material with a flexible armor structure for metal corrosion protection prepared in this invention combines a superhydrophobic layer with a flexible armor structure to construct a micro-nano hierarchical rough structure with ultra-high roughness and ultra-low surface free energy required for superhydrophobic coating materials. Furthermore, the synergistic effect of the superhydrophobic layer and the flexible armor structure not only endows the composite coating with excellent superhydrophobic properties but also effectively improves the mechanical stability and durability of the composite coating. In the grooved structure of the flexible armor structure, a superhydrophobic suspension is sprayed to prepare the superhydrophobic layer. When the coating is subjected to external forces, the flexible armor structure effectively protects the superhydrophobic layer, thereby reducing the degree of damage to the superhydrophobic layer and effectively improving the superhydrophobic mechanical stability and durability of the composite coating.

[0027] 3. The high-stability superhydrophobic composite material with flexible armor structure for metal corrosion protection prepared by the present invention exhibits good superhydrophobic properties in both water droplet contact angle and roll-off angle tests. Furthermore, the high-stability superhydrophobic composite material with flexible armor structure for metal corrosion protection prepared by the present invention can be applied to the surface of various metal substrates and exhibits good superhydrophobic properties.

[0028] 4. The high-stability superhydrophobic composite material with flexible armor structure for metal corrosion protection prepared by the present invention has been verified to have high stability through durability tests (including abrasion resistance test of the coating under 100 g load on 2000 grit sandpaper and tape peeling test under 100 g load).

[0029] 5. The high-stability superhydrophobic composite material with flexible armor structure for metal corrosion protection prepared in this invention has been verified by corrosion resistance tests (including electrochemical impedance spectroscopy (EIS) test and real marine atmospheric environment exposure test, etc.) to have good corrosion resistance on the surface of the metal substrate material.

[0030] 6. The highly stable superhydrophobic composite material with a flexible armor structure for metal corrosion protection prepared by this invention has the advantages of simple preparation technology, easy operation and high efficiency, which is of great significance for the application of superhydrophobic composite materials in actual production. Attached Figure Description

[0031] Figure 1 This is a schematic diagram of the structure of the composite material coating prepared by the present invention;

[0032] Figure 2 These are ordinary optical photographs and contact angle and roll-off angle diagrams of water droplets on the surface of the composite material coating of the sample prepared in Example 1 of this invention. Detailed Implementation

[0033] The present invention will now be described in detail with reference to specific embodiments. These embodiments will help those skilled in the art to further understand the present invention, but do not limit the invention in any way. In particular, it should be noted that those skilled in the art can make changes and improvements without departing from the concept of the present invention. These all fall within the protection scope of the present invention.

[0034] This invention utilizes a combination of flexible rubber particles and an adhesive to construct a flexible armor structure on the surface of a substrate. This structure effectively resists damage to the rough surface structure of the superhydrophobic composite material from external forces, thereby improving the stability and durability of the superhydrophobic composite coating. This results in a more durable overall microstructural integrity and superhydrophobic performance. Through the synergistic effect of the superhydrophobic material and the flexible armor structure, the composite coating exhibits good mechanical stability and superhydrophobic properties.

[0035] The method for preparing the high-stability superhydrophobic composite material of flexible armor structure for metal corrosion protection described in this invention is to obtain it by spraying a superhydrophobic surface layer suspension onto the surface of the flexible armor structure and then completely curing it.

[0036] The flexible armor structure is prepared by: diluting the adhesive in an organic solvent to make a diluent, then spraying the diluent onto the surface of a pre-treated metal substrate to form an adhesive layer, and then uniformly bonding the flexible armor particles to the surface of the adhesive layer. After curing, the flexible armor structure is obtained.

[0037] Specifically, the steps include the following:

[0038] S1. Preparation of superhydrophobic modified nanoparticles: Hydrophilic nanoparticles were ultrasonically dispersed in an organic solvent, and then a low surface energy organosilane coupling agent was added under stirring conditions to obtain superhydrophobic modified nanoparticles.

[0039] S2. Preparation of superhydrophobic suspension by phase separation method: Polyester is completely dissolved in an organic solvent, and then superhydrophobic modified nanoparticles are added under stirring and stirred until completely dispersed. After the superhydrophobic nanoparticles are completely dispersed, a non-solvent is added to induce phase separation. After phase separation is completed, a superhydrophobic suspension is obtained.

[0040] S3. Preparation of flexible armor structure: Epoxy resin adhesive is diluted in an organic solvent to prepare epoxy diluent. Then, the epoxy diluent is sprayed onto the surface of the pretreated metal substrate to obtain an epoxy adhesive layer. Flexible armor particles are then uniformly bonded to the surface of the epoxy adhesive layer and cured to obtain a flexible armor structure.

[0041] S4. Preparation of a highly stable superhydrophobic composite material with a flexible armor structure for metal corrosion protection: The superhydrophobic suspension prepared in S2 is sprayed onto the surface of the flexible armor structure prepared in S3 using a spray gun. After complete curing, a highly stable superhydrophobic composite material with a flexible armor structure for metal corrosion protection is obtained.

[0042] The pretreatment method for the metal substrate is as follows: the surface of the metal substrate is polished with 800-mesh and 1500-mesh SiC sandpaper, then immersed in ethanol for ultrasonic cleaning for 20 min, followed by ultrasonic cleaning with deionized water three times, each time for 10 min, and then dried for later use. For ease of comparison, only Example 3 uses an A5052 aluminum alloy metal substrate; all others use Q235 carbon steel metal substrates for preparation and testing. In practice, stainless steel, aluminum alloy, magnesium alloy, and other metal materials can also be used as substrates. Ethanol is used as the solvent in the examples and comparative examples, but in practice, one or more of ethanol, ethyl acetate, and butyl acetate can also be used; this invention is not limited to these. All solvents and raw materials used in the examples are commercially available. The flexible armor particles are recycled rubber particles from waste tires, purchased from Chenqi Environmental Protection Raw Materials.

[0043] The specific implementation plan is as follows:

[0044] Example 1

[0045] S1. Preparation of superhydrophobic modified nanoparticles: 5.0 g of hydrophilic metal-based nano-alumina particles were dispersed in 30 mL of ethanol and ultrasonically dispersed for 20 min. Then, 1.0 mL of 1H,1H,2H,2H-perfluorodecyltrimethoxysilane was added under magnetic stirring. The mixture was stirred continuously at room temperature for 12 h (this process is to modify the superhydrophilic metal-based nano-alumina particles through the hydrolysis and condensation reaction of fluorosilane). The resulting suspension was dried to obtain superhydrophobic nano-alumina particles.

[0046] S2. Preparation of superhydrophobic suspension by phase separation method: 0.2 g of thermoplastic polyurethane elastomer particles were completely dissolved in 12 mL of ethyl acetate. Then, 0.25 g of superhydrophobic nano-alumina particles were added, and the mixture was magnetically stirred for 3 h to uniformly disperse the superhydrophobic nano-alumina particles. Then, 2 mL of ethanol was added as a non-solvent to achieve non-solvent-induced TPU phase separation. The mixture was magnetically stirred for 15 min and then sonicated for 15 min. Finally, a uniform surface superhydrophobic suspension was successfully prepared.

[0047] S3. Preparation of the flexible armor structure: A diluted solution of adhesive E44 and curing agent polyamide (mass ratio of E44 to polyamide 1:1) was prepared using anhydrous ethanol as the diluent. The diluted solution was sprayed onto the surface of a Q235 carbon steel substrate under a pressure of 0.3 MPa to prepare an adhesive layer. Then, 60-65 mesh recycled rubber granules from waste tires were uniformly bonded to the surface (rubber granule dosage 268 g / m²). 2 Once it has fully solidified, a flexible armor structure is constructed.

[0048] S4. Preparation of a highly stable superhydrophobic composite material for a flexible armor structure used for metal corrosion protection: The superhydrophobic suspension prepared in S2 was 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 volume: 1.0 mL / cm). 2 After complete curing, a highly stable superhydrophobic composite material with a flexible armor structure for metal corrosion protection is obtained.

[0049] The prepared high-stability superhydrophobic composite material with a flexible armor structure for metal corrosion protection (see schematic diagram) Figure 1 Performance testing methods:

[0050] ① Composite material coating wetting performance test: The contact angle and roll-off angle of water droplets on the coating surface were measured using a contact angle meter to determine the superhydrophobic properties of the prepared coating. The droplet and contact angle diagrams are shown in the figure. Figure 2 As shown.

[0051] ②Mechanical stability test of composite material coating: (1) Sandpaper abrasion test: After the prepared coating sample was abraded with 2000 grit sandpaper under a load of 100 g, the contact angle and roll-off angle of the water droplet were measured using a contact angle measuring instrument to determine the superhydrophobicity of the prepared coating after abrasion and to evaluate its mechanical stability. (2) Tape peeling test: 3M tape was pasted on the surface of the prepared coating sample and pressed tightly under a load of 100 g. After being quickly peeled off, the contact angle and roll-off angle of the water droplet were measured using a contact angle measuring instrument to determine the superhydrophobicity of the prepared coating after abrasion and to evaluate its mechanical stability.

[0052] ③ Corrosion resistance test of composite material coating - electrochemical impedance spectroscopy: In a 3.5 wt.% NaCl aqueous solution system, a three-electrode system was used, with a platinum sheet electrode as the counter electrode and an Ag / AgCl electrode as the reference electrode, and the exposed area was 1 cm². 2 The composite material coating (substrate was Q235 carbon steel) was used as the working electrode, and electrochemical impedance spectroscopy was performed using an electrochemical workstation to determine the electrochemical performance of the prepared coating. Example 1 Performance Test Results:

[0053] 1. Wetting properties of composite material coating: The contact angle and roll-off 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 158.7±1.1°, and the roll-off angle was 4.7±0.1° (see...). Figure 2 This demonstrates that the prepared flexible armor structure high-stability superhydrophobic composite material for metal corrosion protection exhibits excellent superhydrophobic properties.

[0054] 2. Mechanical stability test of composite material coating: (1) After the coating was worn for 1200 times under a 100 g load of 2000 grit sandpaper, the water droplet contact angle was greater than 150° and the roll-off angle was less than 10°. Specifically: after 100 wear cycles, the water contact angle of the coating was 155.3±0.3° and the roll-off angle was 5.0±0.3°; after 300 wear cycles, the water contact angle of the coating was 154.4±0.7° and the roll-off angle was 5.7±0.3°; after 600 wear cycles, the water contact angle of the coating was 154.0±1.2° and the roll-off angle was 5.6±0.1°; after 900 wear cycles, the water contact angle of the coating was 153.9±0.7° and the roll-off angle was 5.3±0.3°; after 1200 wear cycles, the water contact angle of the coating was 150.1±0.6° and the roll-off angle was 9.2±0.4°. It can be seen that the high-stability superhydrophobic composite material with flexible armor structure for metal corrosion protection still exhibits good superhydrophobic properties and good mechanical wear resistance after 1200 sandpaper abrasions. (2) After the coating is peeled off by 3M tape 450 times, the water droplet contact angle is greater than 150° and the roll-off angle is less than 10°. Specifically, after 50 peel cycles, the coating's water contact angle was 154.7±0.3° and its roll-off angle was 5.0±0.2°; after 100 peel cycles, the water contact angle was 153.6±0.6° and the roll-off angle was 5.0±0.1°; after 200 peel cycles, the water contact angle was 153.0±0.6° and the roll-off angle was 5.1±0.2°; after 300 peel cycles, the water contact angle was 152.4±1.0° and the roll-off angle was 6.8±0.2°; and after 450 peel cycles, the composite material coating's water contact angle was 150.0±0.2° and the roll-off angle was 9.4±0.4°. This demonstrates that the prepared high-stability superhydrophobic composite material with a flexible armor structure for metal corrosion protection still exhibits good superhydrophobic properties and excellent coating adhesion even after 450 peel cycles with 3M tape.

[0055] 3. Corrosion resistance test of composite material coating - electrochemical impedance spectroscopy: The results show that the charge transfer resistance R of the coating ct =9.53×10 10 Ω cm 2Compared to blank Q235 carbon steel matrix (R ct =1.18×10 3 Ω cm 2 It improved by 7 orders of magnitude, demonstrating better corrosion resistance.

[0056] Example 2

[0057] S1. Preparation of superhydrophobic modified nanoparticles: 5.0 g of superhydrophilic nano-titanium dioxide particles were dispersed in 30 mL of ethanol and ultrasonically dispersed for 20 min. Then, 1.0 mL of 1H,1H,2H,2H-perfluorodecyltrimethoxysilane was added under magnetic stirring and stirred continuously at room temperature for 12 h (this process is to modify the superhydrophilic nano-titanium dioxide particles through the hydrolysis and condensation reaction of fluorosilane). The resulting suspension was dried to obtain superhydrophobic nano-titanium dioxide particles.

[0058] S2. Preparation of superhydrophobic suspension by phase separation method: 0.2 g of thermoplastic polyurethane elastomer particles were completely dissolved in 12 mL of ethyl acetate. Then, 0.25 g of superhydrophobic nano-titanium dioxide particles were added, and the mixture was magnetically stirred for 3 h to uniformly disperse the superhydrophobic nano-titanium dioxide particles. Then, 2 mL of ethanol was added as a non-solvent to achieve non-solvent-induced TPU phase separation. The mixture was magnetically stirred for 15 min and sonicated for 15 min. Finally, a uniform surface superhydrophobic suspension was successfully prepared.

[0059] S3. Preparation of the flexible armor structure: A diluted solution of adhesive E44 and curing agent polyamide (mass ratio of E44 to polyamide 1:1) was prepared using anhydrous ethanol as the diluent. The diluted solution was sprayed onto the surface of a Q235 carbon steel substrate under a pressure of 0.3 MPa to prepare an adhesive layer. Then, 60-65 mesh recycled rubber granules from waste tires were uniformly bonded to the surface (rubber granule dosage 268 g / m²). 2 Once it has fully solidified, a flexible armor structure is constructed.

[0060] S4. Preparation of a highly stable superhydrophobic composite material for a flexible armor structure used for metal corrosion protection: The superhydrophobic suspension prepared in S2 was 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 volume: 1.0 mL / cm). 2 After complete curing, a highly stable superhydrophobic composite material with a flexible armor structure for metal corrosion protection is obtained.

[0061] The performance testing method for the highly stable superhydrophobic composite material with a flexible armor structure for metal corrosion protection obtained in Example 2 is the same as that in Example 1. The test results are as follows:

[0062] 1. Wetting properties of composite material coating: The contact angle and roll-off 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 roll-off angle was 4.3°. It can be seen that the high-stability superhydrophobic composite material with flexible armor structure for metal corrosion protection prepared exhibits excellent superhydrophobic properties.

[0063] 2. Mechanical stability test of composite material coating: (1) After 1200 abrasion cycles under a 100 g load of 2000 grit sandpaper, the water droplet contact angle of the coating is greater than 150° and the roll-off angle is less than 10°. It can be seen that the high-stability superhydrophobic composite material with flexible armor structure for metal corrosion protection still exhibits good superhydrophobic properties for water droplets after 1200 abrasion cycles of sandpaper, and has good mechanical wear resistance. (2) After 450 peel cycles of 3M tape, the water droplet contact angle of the coating is greater than 150° and the roll-off angle is less than 10°. It can be seen that the high-stability superhydrophobic composite material with flexible armor structure for metal corrosion protection still exhibits good superhydrophobic properties for water droplets after 450 peel cycles of 3M tape, and has good coating adhesion.

[0064] 3. Corrosion resistance test of composite material coating - electrochemical impedance spectroscopy: The results show that the charge transfer resistance R of the coating ct =8.74×10 10 Ω cm 2 Compared to blank Q235 carbon steel matrix (R ct =1.18×10 3 Ω cm 2 It improved by 7 orders of magnitude, demonstrating better corrosion resistance.

[0065] Example 3

[0066] S1. Preparation of superhydrophobic modified nanoparticles: 5.0 g of hydrophilic metal-based nano-alumina particles were dispersed in 30 mL of ethanol and ultrasonically dispersed for 20 min. Then, 1.0 mL of 1H,1H,2H,2H-perfluorooctyltrimethoxysilane was added under magnetic stirring. The mixture was stirred continuously at room temperature for 12 h (this process is to modify the superhydrophilic metal-based nano-alumina particles through the hydrolysis and condensation reaction of fluorosilane). The resulting suspension was dried to obtain superhydrophobic nano-alumina particles.

[0067] S2. Preparation of superhydrophobic suspension by phase separation method: 0.2 g of thermoplastic polyurethane elastomer particles were completely dissolved in 12 mL of ethyl acetate. Then, 0.25 g of superhydrophobic nano-alumina particles were added, and the mixture was magnetically stirred for 3 h to uniformly disperse the superhydrophobic nano-alumina particles. Then, 2 mL of ethanol was added as a non-solvent to achieve non-solvent-induced TPU phase separation. The mixture was magnetically stirred for 15 min and then sonicated for 15 min. Finally, a uniform surface superhydrophobic suspension was successfully prepared.

[0068] S3. Preparation of the flexible armor structure: A diluted solution of adhesive E44 and curing agent polyamide (mass ratio of E44 to polyamide 1:1) was prepared using anhydrous ethanol as the diluent. The diluted solution was sprayed onto the surface of a Q235 carbon steel substrate under a pressure of 0.3 MPa to prepare an adhesive layer. Then, 60-65 mesh recycled rubber granules from waste tires were uniformly bonded to the surface (rubber granule dosage 268 g / m²). 2 Once it has fully solidified, a flexible armor structure is constructed.

[0069] S4. Preparation of a highly stable superhydrophobic composite material for a flexible armor structure used for metal corrosion protection: The superhydrophobic suspension prepared in S2 was 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 volume: 1.0 mL / cm). 2 After complete curing, a highly stable superhydrophobic composite material with a flexible armor structure for metal corrosion protection is obtained.

[0070] The performance testing method for the highly stable superhydrophobic composite material with a flexible armor structure for metal corrosion protection obtained in Example 3 is the same as that in Example 1. The test results are as follows:

[0071] 1. Coating wetting properties: The contact angle and roll-off 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 roll-off angle was 5.1°. It can be seen that the high-stability superhydrophobic composite material with flexible armor structure for metal corrosion protection prepared exhibits excellent superhydrophobic properties.

[0072] 2. Coating mechanical stability test: (1) After 1200 abrasion cycles under a 100 g load of 2000 grit sandpaper, the water droplet contact angle of the coating is greater than 150° and the roll-off angle is less than 10°. It can be seen that the high-stability superhydrophobic composite material with flexible armor structure for metal corrosion protection still exhibits good superhydrophobic properties for water droplets after 1200 abrasion cycles of sandpaper, and has good mechanical wear resistance. (2) After 450 peel cycles of 3M tape, the water droplet contact angle of the coating is greater than 150° and the roll-off angle is less than 10°. It can be seen that the high-stability superhydrophobic composite material with flexible armor structure for metal corrosion protection still exhibits good superhydrophobic properties for water droplets after 450 peel cycles of 3M tape, and has good coating adhesion.

[0073] 3. Coating corrosion resistance test - electrochemical impedance spectroscopy test: The results show that the charge transfer resistance R of the coating ct =9.62×10 9 Ω cm 2 Compared to Q235 carbon steel substrate (R ct =1.18×10 3 Ω cm 2 It improved by 6 orders of magnitude, demonstrating better corrosion resistance.

[0074] Example 4

[0075] S1. Preparation of superhydrophobic modified nanoparticles: 5.0 g of hydrophilic metal-based nano-alumina particles were dispersed in 30 mL of ethanol and ultrasonically dispersed for 20 min. Then, 1.0 mL of 1H,1H,2H,2H-perfluorodecyltrimethoxysilane was added under magnetic stirring. The mixture was stirred continuously at room temperature for 12 h (this process is to modify the superhydrophilic metal-based nano-alumina particles through the hydrolysis and condensation reaction of fluorosilane). The resulting suspension was dried to obtain superhydrophobic nano-alumina particles.

[0076] S2. Preparation of superhydrophobic suspension by phase separation method: 0.2 g of thermoplastic polyurethane elastomer particles were completely dissolved in 12 mL of ethyl acetate. Then, 0.25 g of superhydrophobic nano-alumina particles were added, and the mixture was magnetically stirred for 3 h to uniformly disperse the superhydrophobic nano-alumina particles. Then, 2 mL of ethanol was added as a non-solvent to achieve non-solvent-induced TPU phase separation. The mixture was magnetically stirred for 15 min and then sonicated for 15 min. Finally, a uniform surface superhydrophobic suspension was successfully prepared.

[0077] S3. Preparation of the flexible armor structure: A diluted solution of adhesive E44 and curing agent polyamide (mass ratio of E44 to polyamide 1:1) was prepared using anhydrous ethanol as the diluent. The diluted solution was sprayed onto the surface of an A5083 aluminum alloy substrate under a pressure of 0.3 MPa to prepare an adhesive layer. Then, 60-65 mesh recycled rubber granules from waste tires were uniformly bonded to the surface (rubber granule dosage 268 g / m²). 2 Once it has fully solidified, a flexible armor structure is constructed.

[0078] S4. Preparation of a highly stable superhydrophobic composite material for a flexible armor structure used for metal corrosion protection: The superhydrophobic suspension prepared in S2 was 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 volume: 1.0 mL / cm). 2 After complete curing, a highly stable superhydrophobic composite material with a flexible armor structure for metal corrosion protection is obtained.

[0079] The performance testing method for the highly stable superhydrophobic composite material with a flexible armor structure for metal corrosion protection obtained in Example 4 is the same as that in Example 1. The test results are as follows:

[0080] 1. Coating wetting properties: The contact angle and roll-off 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 roll-off angle was 4.6°. It can be seen that the high-stability superhydrophobic composite material with flexible armor structure for metal corrosion protection prepared exhibits excellent superhydrophobic properties.

[0081] 2. Coating mechanical stability test: (1) After 1200 abrasion cycles under a 100 g load of 2000 grit sandpaper, the water droplet contact angle of the coating is greater than 150° and the roll-off angle is less than 10°. It can be seen that the high-stability superhydrophobic composite material with flexible armor structure for metal corrosion protection still exhibits good superhydrophobic properties for water droplets after 1200 abrasion cycles of sandpaper, and has good mechanical wear resistance. (2) After 450 peel cycles of 3M tape, the water droplet contact angle of the coating is greater than 150° and the roll-off angle is less than 10°. It can be seen that the high-stability superhydrophobic composite material with flexible armor structure for metal corrosion protection still exhibits good superhydrophobic properties for water droplets after 450 peel cycles of 3M tape, and has good coating adhesion.

[0082] 3. Coating corrosion resistance test - electrochemical impedance spectroscopy test: The results show that the charge transfer resistance R of the coating ct =1.21×10 11 Ω cm 2 Compared to blank A5083 aluminum alloy substrate (R ct =1.25×104 Ω cm 2 It improved by 7 orders of magnitude, demonstrating better corrosion resistance.

[0083] Example 5

[0084] S1. Preparation of superhydrophobic modified nanoparticles: 5.0 g of hydrophilic metal-based nano-alumina particles were dispersed in 30 mL of ethanol and ultrasonically dispersed for 20 min. Then, 1.0 mL of 1H,1H,2H,2H-perfluorodecyltrimethoxysilane was added under magnetic stirring. The mixture was stirred continuously at room temperature for 12 h (this process is to modify the superhydrophilic metal-based nano-alumina particles through the hydrolysis and condensation reaction of fluorosilane). The resulting suspension was dried to obtain superhydrophobic nano-alumina particles.

[0085] S2. Preparation of superhydrophobic suspension by phase separation method: 0.2 g of Si-modified polyurethane (Si-PU) was completely dissolved in 12 mL of ethyl acetate. Then, 0.25 g of superhydrophobic nano-alumina particles were added, and the mixture was magnetically stirred for 3 h to uniformly disperse the superhydrophobic nano-alumina particles. Then, 2 mL of ethanol was added as a non-solvent to achieve non-solvent-induced TPU phase separation. The mixture was magnetically stirred for 15 min and then sonicated for 15 min. Finally, a uniform surface superhydrophobic suspension was successfully prepared.

[0086] S3. Preparation of the flexible armor structure: A diluted solution of adhesive E44 and curing agent polyamide (mass ratio of E44 to polyamide 1:1) was prepared using anhydrous ethanol as the diluent. The diluted solution was sprayed onto the surface of a Q235 carbon steel substrate under a pressure of 0.3 MPa to prepare an adhesive layer. Then, 60-65 mesh recycled rubber granules from waste tires were uniformly bonded to the surface (rubber granule dosage 268 g / m²). 2 Once it has fully solidified, a flexible armor structure is constructed.

[0087] S4. Preparation of a highly stable superhydrophobic composite material for a flexible armor structure used for metal corrosion protection: The superhydrophobic suspension prepared in S2 was 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 volume: 1.0 mL / cm). 2 After complete curing, a highly stable superhydrophobic composite material with a flexible armor structure for metal corrosion protection is obtained.

[0088] The performance testing method for the highly stable superhydrophobic composite material with a flexible armor structure for metal corrosion protection obtained in Example 5 is the same as that in Example 1. The test results are as follows:

[0089] 1. Coating wetting properties: The contact angle and roll-off 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 157.8° and the roll-off angle was 4.8°. It can be seen that the high-stability superhydrophobic composite material with flexible armor structure for metal corrosion protection prepared exhibits excellent superhydrophobic properties.

[0090] 2. Coating mechanical stability test: (1) After 1200 abrasion cycles under a 100 g load of 2000 grit sandpaper, the water droplet contact angle of the coating is greater than 150° and the roll-off angle is less than 10°. It can be seen that the high-stability superhydrophobic composite material with flexible armor structure for metal corrosion protection still exhibits good superhydrophobic properties for water droplets after 1200 abrasion cycles of sandpaper, and has good mechanical wear resistance. (2) After 450 peel cycles of 3M tape, the water droplet contact angle of the coating is greater than 150° and the roll-off angle is less than 10°. It can be seen that the high-stability superhydrophobic composite material with flexible armor structure for metal corrosion protection still exhibits good superhydrophobic properties for water droplets after 450 peel cycles of 3M tape, and has good coating adhesion.

[0091] 3. Coating corrosion resistance test - electrochemical impedance spectroscopy test: The results show that the charge transfer resistance R of the coating ct =8.23×10 10 Ω cm 2 Compared to blank Q235 carbon steel matrix (R ct =1.18×10 3 Ω cm 2 It improved by 7 orders of magnitude, demonstrating better corrosion resistance.

[0092] Example 6

[0093] S1. Preparation of superhydrophobic modified nanoparticles: 15.0 g of hydrophilic metal-based nano-alumina particles were dispersed in 100 mL of ethanol and ultrasonically dispersed for 20 min. Then, 5.0 mL of 1H,1H,2H,2H-perfluorodecyltrimethoxysilane was added under magnetic stirring. The mixture was stirred continuously at room temperature for 12 h (this process is to modify the superhydrophilic metal-based nano-alumina particles through the hydrolysis and condensation reaction of fluorosilane). The resulting suspension was dried to obtain superhydrophobic nano-alumina particles.

[0094] S2. Preparation of superhydrophobic suspension by phase separation method: 0.2 g of thermoplastic polyurethane elastomer particles were completely dissolved in 12 mL of ethyl acetate. Then, 0.25 g of superhydrophobic nano-alumina particles were added, and the mixture was magnetically stirred for 3 h to uniformly disperse the superhydrophobic nano-alumina particles. Then, 2 mL of ethanol was added as a non-solvent to achieve non-solvent-induced TPU phase separation. The mixture was magnetically stirred for 15 min and then sonicated for 15 min. Finally, a uniform surface superhydrophobic suspension was successfully prepared.

[0095] S3. Preparation of the flexible armor structure: A diluted solution of adhesive E44 and curing agent polyamide (mass ratio of E44 to polyamide 1:1) was prepared using anhydrous ethanol as the diluent. The diluted solution was sprayed onto the surface of a Q235 carbon steel substrate under a pressure of 0.3 MPa to prepare an adhesive layer. Then, 60-65 mesh recycled rubber granules from waste tires were uniformly bonded to the surface (rubber granule dosage 268 g / m²). 2 Once it has fully solidified, a flexible armor structure is constructed.

[0096] S4. Preparation of a highly stable superhydrophobic composite material for a flexible armor structure used for metal corrosion protection: The superhydrophobic suspension prepared in S2 was 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 volume: 1.0 mL / cm). 2 After complete curing, a highly stable superhydrophobic composite material with a flexible armor structure for metal corrosion protection is obtained.

[0097] The performance testing method for the highly stable superhydrophobic composite material with a flexible armor structure for metal corrosion protection obtained in Example 6 is the same as that in Example 1. The test results are as follows:

[0098] 1. Coating wetting performance: The contact angle and roll-off 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 roll-off angle was 4.3°. It can be seen that the high-stability superhydrophobic composite material with flexible armor structure for metal corrosion protection prepared exhibits excellent superhydrophobic properties.

[0099] 2. Coating mechanical stability test: (1) After 1200 abrasion cycles under a 100 g load of 2000 grit sandpaper, the water droplet contact angle of the coating is greater than 150° and the roll-off angle is less than 10°. It can be seen that the high-stability superhydrophobic composite material with flexible armor structure for metal corrosion protection still exhibits good superhydrophobic properties for water droplets after 1200 abrasion cycles of sandpaper, and has good mechanical wear resistance. (2) After 450 peel cycles of 3M tape, the water droplet contact angle of the coating is greater than 150° and the roll-off angle is less than 10°. It can be seen that the high-stability superhydrophobic composite material with flexible armor structure for metal corrosion protection still exhibits good superhydrophobic properties for water droplets after 450 peel cycles of 3M tape, and has good coating adhesion.

[0100] 3. Coating corrosion resistance test - electrochemical impedance spectroscopy test: The results show that the charge transfer resistance R of the coating ct =9.15×10 10 Ω cm 2 Compared to blank Q235 carbon steel matrix (R ct =1.18×10 3 Ω cm 2 It improved by 7 orders of magnitude, demonstrating better corrosion resistance.

[0101] Example 7

[0102] S1. Preparation of superhydrophobic modified nanoparticles: 5.0 g of hydrophilic metal-based nano-alumina particles were dispersed in 30 mL of ethanol and ultrasonically dispersed for 20 min. Then, 1.0 mL of 1H,1H,2H,2H-perfluorodecyltrimethoxysilane was added under magnetic stirring. The mixture was stirred continuously at room temperature for 12 h (this process is to modify the superhydrophilic metal-based nano-alumina particles through the hydrolysis and condensation reaction of fluorosilane). The resulting suspension was dried to obtain superhydrophobic nano-alumina particles.

[0103] S2. Preparation of superhydrophobic suspension by phase separation method: 0.2 g of thermoplastic polyurethane elastomer particles were completely dissolved in 12 mL of ethyl acetate. Then, 0.25 g of superhydrophobic nano-alumina particles were added, and the mixture was magnetically stirred for 3 h to uniformly disperse the superhydrophobic nano-alumina particles. Then, 1.5 mL of ethanol was added as a non-solvent to achieve non-solvent-induced TPU phase separation. The mixture was magnetically stirred for 15 min and sonicated for 15 min. Finally, a uniform surface superhydrophobic suspension was successfully prepared.

[0104] S3. Preparation of the flexible armor structure: A diluted solution of adhesive E44 and curing agent polyamide (mass ratio of E44 to polyamide 1:1) was prepared using anhydrous ethanol as the diluent. The diluted solution was sprayed onto the surface of a Q235 carbon steel substrate under a pressure of 0.3 MPa to prepare an adhesive layer. Then, 60-65 mesh recycled rubber granules from waste tires were uniformly bonded to the surface (rubber granule dosage 268 g / m²). 2 Once it has fully solidified, a flexible armor structure is constructed.

[0105] S4. Preparation of a highly stable superhydrophobic composite material for a flexible armor structure used for metal corrosion protection: The superhydrophobic suspension prepared in S2 was 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 volume: 1.0 mL / cm). 2 After complete curing, a highly stable superhydrophobic composite material with a flexible armor structure for metal corrosion protection is obtained.

[0106] The performance testing method for the highly stable superhydrophobic composite material with a flexible armor structure for metal corrosion protection obtained in Example 7 is the same as that in Example 1. The test results are as follows:

[0107] 1. Coating wetting properties: The contact angle and roll-off 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 roll-off angle was 5.3°. It can be seen that the high-stability superhydrophobic composite material with flexible armor structure for metal corrosion protection prepared exhibits excellent superhydrophobic properties.

[0108] 2. Coating mechanical stability test: (1) After 1200 abrasion cycles under a 100 g load of 2000 grit sandpaper, the water droplet contact angle of the coating is greater than 150° and the roll-off angle is less than 10°. It can be seen that the high-stability superhydrophobic composite material with flexible armor structure for metal corrosion protection still exhibits good superhydrophobic properties for water droplets after 1200 abrasion cycles of sandpaper, and has good mechanical wear resistance. (2) After 450 peel cycles of 3M tape, the water droplet contact angle of the coating is greater than 150° and the roll-off angle is less than 10°. It can be seen that the high-stability superhydrophobic composite material with flexible armor structure for metal corrosion protection still exhibits good superhydrophobic properties for water droplets after 450 peel cycles of 3M tape, and has good coating adhesion.

[0109] 3. Coating corrosion resistance test - electrochemical impedance spectroscopy test: The results show that the charge transfer resistance R of the coating ct =8.07×10 10 Ω cm 2 Compared to blank Q235 carbon steel matrix (R ct =1.18×103 Ω cm 2 It improved by 7 orders of magnitude, demonstrating better corrosion resistance.

[0110] Example 8

[0111] S1. Preparation of superhydrophobic modified nanoparticles: 5.0 g of hydrophilic metal-based nano-alumina particles were dispersed in 30 mL of ethanol and ultrasonically dispersed for 20 min. Then, 1.0 mL of 1H,1H,2H,2H-perfluorodecyltrimethoxysilane was added under magnetic stirring. The mixture was stirred continuously at room temperature for 12 h (this process is to modify the superhydrophilic metal-based nano-alumina particles through the hydrolysis and condensation reaction of fluorosilane). The resulting suspension was dried to obtain superhydrophobic nano-alumina particles.

[0112] S2. Preparation of superhydrophobic suspension by phase separation method: 0.2 g of thermoplastic polyurethane elastomer particles were completely dissolved in 12 mL of ethyl acetate. Then, 0.25 g of superhydrophobic nano-alumina particles were added, and the mixture was magnetically stirred for 3 h to uniformly disperse the superhydrophobic nano-alumina particles. Then, 2.0 mL of ethanol was added as a non-solvent to achieve non-solvent-induced TPU phase separation. The mixture was magnetically stirred for 15 min and sonicated for 15 min. Finally, a uniform surface superhydrophobic suspension was successfully prepared.

[0113] S3. Preparation of the flexible armor structure: A diluted solution of adhesive E44 and curing agent polyetheramine (D230) was prepared using anhydrous ethanol as the diluent (mass ratio of E44 to polyetheramine was 1:1). The diluted solution was sprayed onto the surface of a Q235 carbon steel substrate under a pressure of 0.3 MPa to prepare an adhesive layer. Then, 60-65 mesh recycled rubber granules from waste tires were uniformly bonded to the surface (rubber granule dosage 268 g / m²). 2 Once it has fully solidified, a flexible armor structure is constructed.

[0114] S4. Preparation of a highly stable superhydrophobic composite material for a flexible armor structure used for metal corrosion protection: The superhydrophobic suspension prepared in S2 was 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 volume: 1.0 mL / cm). 2 After complete curing, a highly stable superhydrophobic composite material with a flexible armor structure for metal corrosion protection is obtained.

[0115] The performance testing method for the highly stable superhydrophobic composite material with a flexible armor structure for metal corrosion protection obtained in Example 7 is the same as that in Example 1. The test results are as follows:

[0116] 1. Coating wetting performance: The contact angle and roll-off 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 roll-off angle was 4.9°. It can be seen that the high-stability superhydrophobic composite material with flexible armor structure for metal corrosion protection prepared exhibits excellent superhydrophobic properties.

[0117] 2. Coating mechanical stability test: (1) After 1200 abrasion cycles under a 100 g load of 2000 grit sandpaper, the water droplet contact angle of the coating is greater than 150° and the roll-off angle is less than 10°. It can be seen that the high-stability superhydrophobic composite material with flexible armor structure for metal corrosion protection still exhibits good superhydrophobic properties for water droplets after 1200 abrasion cycles of sandpaper, and has good mechanical wear resistance. (2) After 450 peel cycles of 3M tape, the water droplet contact angle of the coating is greater than 150° and the roll-off angle is less than 10°. It can be seen that the high-stability superhydrophobic composite material with flexible armor structure for metal corrosion protection still exhibits good superhydrophobic properties for water droplets after 450 peel cycles of 3M tape, and has good coating adhesion.

[0118] 3. Coating corrosion resistance test - electrochemical impedance spectroscopy test: The results show that the charge transfer resistance R of the coating ct =9.11×10 10 Ω cm 2 Compared to blank Q235 carbon steel matrix (R ct =1.18×10 3 Ω cm 2 It improved by 7 orders of magnitude, demonstrating better corrosion resistance.

[0119] Comparative Example 1

[0120] 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. After continuous stirring at room temperature for 12 h (this process is to modify the superhydrophilic metal-based nano aluminum oxide particles through the hydrolysis and condensation reaction of fluorosilane), dry the resulting suspension to obtain superhydrophobic nano aluminum oxide particles.

[0121] 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-alumina particles and stir magnetically for 3 h to uniformly disperse the superhydrophobic nano-alumina 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 superhydrophobic suspension was successfully prepared. Spray this suspension onto the surface of a Q235 carbon steel substrate to obtain a surface superhydrophobic coating.

[0122] The performance testing method for the comparative coating sample obtained in Comparative Example 1 is the same as that in Example 1, and the test results are as follows:

[0123] 1. Coating wetting performance: Water droplets were placed on the coating surface and measured using a contact angle meter. The water contact angle of the coating surface was 159.3° and the roll-off angle was 3.8°. This shows that the prepared superhydrophobic coating itself has excellent superhydrophobic properties.

[0124] 2. Mechanical stability test of coating: (1) After 85 wear cycles under a 100 g load of 2000 grit sandpaper, the water droplet contact angle of the coating is less than 150° and the roll-off angle is greater than 10°. It can be seen that the prepared superhydrophobic coating loses its superhydrophobic properties after a certain degree of wear and has poor mechanical wear resistance. (2) After 40 peel cycles of 3M tape, the water droplet contact angle of the coating is less than 150° and the roll-off angle is greater than 10°. It can be seen that the prepared superhydrophobic coating loses its superhydrophobic properties after a certain degree of tape peel and has 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 of the coating ct =8.69×10 7 Ω cm 2 Compared to the highly stable superhydrophobic composite material with a flexible armor structure used for metal corrosion protection in Example 1 (R... ct =9.53×10 10 Ω cm 2 The electrochemical performance was reduced by three orders of magnitude, and the corrosion resistance was significantly reduced.

[0126] As can be seen from the test results of Comparative Example 1, the mechanical wear resistance of the coating is significantly reduced and the corrosion resistance is significantly decreased due to the absence of epoxy adhesive layer and flexible armor structure. However, the mechanical wear resistance and corrosion resistance of the composite material coating of this invention are significantly improved by introducing epoxy adhesive layer and flexible armor structure.

[0127] Comparative Example 2

[0128] 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. After continuous stirring at room temperature for 12 h (this process is to modify the superhydrophilic metal-based nano aluminum oxide particles through the hydrolysis and condensation reaction of fluorosilane), dry the resulting suspension to obtain superhydrophobic nano aluminum oxide particles.

[0129] 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-alumina particles and stir magnetically for 3 h to uniformly disperse the superhydrophobic nano-alumina 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 superhydrophobic suspension with a surface layer was successfully prepared.

[0130] 3. Measure epoxy resin and its curing agent polyamide (650) at a weight ratio of 1:1 and dilute them in 20 mL of ethanol under magnetic stirring to prepare epoxy diluent. Then, use a spray gun to spray the epoxy diluent onto the surface of the pretreated Q235 carbon steel substrate material. Subsequently, spray the superhydrophobic suspension onto its surface to obtain a superhydrophobic coating with an epoxy bonding layer and a superhydrophobic surface layer.

[0131] The performance testing 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:

[0132] 1. Coating wetting properties: Water droplets were placed on the coating surface and measured using a contact angle meter. The water contact angle of the coating surface was 158.9° and the roll-off angle was 4.0°. This shows that the prepared coating has excellent superhydrophobic properties.

[0133] 2. Mechanical stability test of coating: (1) After 130 wear cycles under a 100 g load of 2000 grit sandpaper, the water droplet contact angle of the coating is less than 150° and the roll-off angle is greater than 10°. It can be seen that the prepared superhydrophobic coating loses its superhydrophobic properties after a certain degree of wear and has poor mechanical wear resistance. (2) After 60 peel cycles of 3M tape, the water droplet contact angle of the coating is less than 150° and the roll-off angle is greater than 10°. It can be seen that the prepared superhydrophobic coating loses its superhydrophobic properties after a certain degree of tape peel and has poor adhesion between the coating and the substrate.

[0134] 3. Coating corrosion resistance test - electrochemical impedance spectroscopy test: The results show that the charge transfer resistance R of the coating ct =9.66×10 8 Ω cm2 Compared to the highly stable superhydrophobic composite material with a flexible armor structure used for metal corrosion protection in Example 1 (R... ct =9.53×10 10 Ω cm 2 The electrochemical performance was reduced by two orders of magnitude, and the corrosion resistance was significantly reduced.

[0135] As can be seen from the test results of Comparative Example 2, the mechanical wear resistance of the coating is significantly reduced and the corrosion resistance is significantly decreased due to the lack of a flexible armor structure. However, the mechanical wear resistance and corrosion resistance of the composite material coating are significantly improved by introducing a flexible armor structure.

[0136] Comparative Example 3

[0137] 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. After continuous stirring at room temperature for 12 h (this process is to modify the superhydrophilic metal-based nano aluminum oxide particles through the hydrolysis and condensation reaction of fluorosilane), dry the resulting suspension to obtain superhydrophobic nano aluminum oxide particles.

[0138] 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-alumina particles and stir magnetically for 3 h to uniformly disperse the superhydrophobic nano-alumina 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 superhydrophobic suspension with a surface layer was successfully prepared.

[0139] 3. A diluted solution of adhesive E44 and curing agent polyamide (mass ratio of E44 to polyamide 1:1) was prepared using anhydrous ethanol as the diluent. The diluted solution was sprayed onto the surface of a Q235 carbon steel substrate under a pressure of 0.3 MPa to prepare an adhesive layer. Then, 60-65 mesh recycled rubber granules from waste tires were uniformly bonded to the surface (rubber granule dosage 268 g / m²). 2 Once it has fully solidified, a flexible armor structure is constructed.

[0140] 4. Apply the superhydrophobic suspension prepared in step 2 to the surface of the flexible armor structure prepared in step 3 using a spray gun (spraying pressure: 0.3 MPa, spraying distance: 15 cm, suspension volume: 1.0 mL / cm). 2 After complete curing, a control coating sample was obtained.

[0141] The performance testing method for the comparative coating sample obtained in Comparative Example 3 is the same as that in Example 1, and the test results are as follows:

[0142] Coating wetting properties: Water droplets were placed on the coating surface and measured using a contact angle meter. The water contact angle of the coating surface was 136.1°, indicating that the prepared control coating sample did not have superhydrophobic properties.

[0143] The test results of Comparative Example 3 show that the amount of hydrophobic modified nanoparticles has a significant impact on the superhydrophobic performance of the coating. If the concentration is too low, the coating sample will not be able to achieve superhydrophobic performance.

[0144] Comparative Example 4

[0145] 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 0.1 mL of 1H,1H,2H,2H-perfluorodecyltrimethoxysilane under magnetic stirring. Stir continuously at room temperature for 12 h (this process is to modify the superhydrophilic metal-based nano aluminum oxide particles through the hydrolysis and condensation reaction of fluorosilane). Dry the resulting suspension to obtain superhydrophobic nano aluminum oxide particles.

[0146] 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-alumina particles and stir magnetically for 3 h to uniformly disperse the superhydrophobic nano-alumina 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 superhydrophobic suspension with a surface layer was successfully prepared.

[0147] 3. A diluted solution of adhesive E44 and curing agent polyamide (mass ratio of E44 to polyamide 1:1) was prepared using anhydrous ethanol as the diluent. The diluted solution was sprayed onto the surface of a Q235 carbon steel substrate under a pressure of 0.3 MPa to prepare an adhesive layer. Then, 60-65 mesh recycled rubber granules from waste tires were uniformly bonded to the surface (rubber granule dosage 268 g / m²). 2 Once it has fully solidified, a flexible armor structure is constructed.

[0148] 4. Apply the superhydrophobic suspension prepared in step 2 to the surface of the flexible armor structure prepared in step 3 using a spray gun (spraying pressure: 0.3 MPa, spraying distance: 15 cm, suspension volume: 1.0 mL / cm). 2 After complete curing, a control coating sample was obtained.

[0149] The performance testing method for the comparative coating sample obtained in Comparative Example 4 is the same as that in Example 1, and the test results are as follows:

[0150] Coating wetting properties: Water droplets were placed on the coating surface and measured using a contact angle meter. The water contact angle of the coating surface was 132.6°, indicating that the prepared control coating sample did not have superhydrophobic properties.

[0151] The test results of Comparative Example 4 show that the amount of hydrophobic modifier has a significant impact on the superhydrophobic performance of the coating. If the amount is too low, the coating sample will not be able to achieve superhydrophobic performance.

[0152] Comparative Example 5

[0153] 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. Stir continuously at room temperature for 1 h (this process is to modify the superhydrophilic metal-based nano aluminum oxide particles through the hydrolysis and condensation reaction of fluorosilane). Dry the resulting suspension to obtain superhydrophobic nano aluminum oxide particles.

[0154] 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-alumina particles and stir magnetically for 3 h to uniformly disperse the superhydrophobic nano-alumina 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 superhydrophobic suspension with a surface layer was successfully prepared.

[0155] 3. A diluted solution of adhesive E44 and curing agent polyamide (mass ratio of E44 to polyamide 1:1) was prepared using anhydrous ethanol as the diluent. The diluted solution was sprayed onto the surface of a Q235 carbon steel substrate under a pressure of 0.3 MPa to prepare an adhesive layer. Then, 60-65 mesh recycled rubber granules from waste tires were uniformly bonded to the surface (rubber granule dosage 268 g / m²). 2 Once it has fully solidified, a flexible armor structure is constructed.

[0156] 4. Apply the superhydrophobic suspension prepared in step 2 to the surface of the flexible armor structure prepared in step 3 using a spray gun (spraying pressure: 0.3 MPa, spraying distance: 15 cm, suspension volume: 1.0 mL / cm). 2 After complete curing, a control coating sample was obtained.

[0157] The performance testing method for the comparative coating sample obtained in Comparative Example 5 is the same as that in Example 1, and the test results are as follows:

[0158] Coating wetting properties: Water droplets were placed on the coating surface and measured using a contact angle meter. The water contact angle of the coating surface was 141.3°, indicating that the prepared control coating sample did not have superhydrophobic properties.

[0159] The test results of Comparative Example 5 show that the reaction time of low surface energy modification has a great influence on the superhydrophobic modification of nanoparticles. If the time is too short, the coating will not be able to achieve superhydrophobic performance.

[0160] Comparative Example 6

[0161] 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. After continuous stirring at room temperature for 12 h (this process is to modify the superhydrophilic metal-based nano aluminum oxide particles through the hydrolysis and condensation reaction of fluorosilane), dry the resulting suspension to obtain superhydrophobic nano aluminum oxide particles.

[0162] 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-alumina particles and stir magnetically for 3 h to uniformly disperse the superhydrophobic nano-alumina 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 superhydrophobic suspension with a surface layer was successfully prepared.

[0163] 3. A diluted solution of adhesive E44 and curing agent polyamide (mass ratio of E44 to polyamide 1:1) was prepared using anhydrous ethanol as the diluent. The diluted solution was sprayed onto the surface of a Q235 carbon steel substrate under a pressure of 0.3 MPa to prepare an adhesive layer. Then, 100-110 mesh recycled rubber granules from waste tires were uniformly bonded to the surface (rubber granule dosage 268 g / m²). 2 Once it has fully solidified, a flexible armor structure is constructed.

[0164] 4. Apply the superhydrophobic suspension prepared in step 2 to the surface of the flexible armor structure prepared in step 3 using a spray gun (spraying pressure: 0.3 MPa, spraying distance: 15 cm, suspension volume: 1.0 mL / cm). 2 After complete curing, a control coating sample was obtained.

[0165] The performance testing method for the comparative coating sample obtained in Comparative Example 6 is the same as that in Example 1, and the test results are as follows:

[0166] 1. Coating wetting properties: Water droplets were placed on the coating surface and measured using a contact angle meter. The water contact angle of the coating surface was 156.7° and the roll-off angle was 5.1°. This shows that the prepared coating has excellent superhydrophobic properties.

[0167] 2. Mechanical stability test of coating: (1) After 180 wear cycles under a 100 g load of 2000 grit sandpaper, the water droplet contact angle of the coating is less than 150° and the roll-off angle is greater than 10°. It can be seen that the prepared superhydrophobic coating loses its superhydrophobic properties after a certain degree of wear and has poor mechanical wear resistance. (2) After 85 peel cycles of 3M tape, the water droplet contact angle of the coating is less than 150° and the roll-off angle is greater than 10°. It can be seen that the prepared superhydrophobic coating loses its superhydrophobic properties after a certain degree of tape peel and has poor adhesion between the coating and the substrate.

[0168] 3. Coating corrosion resistance test - electrochemical impedance spectroscopy test: The results show that the charge transfer resistance R of the coating ct =6.92×10 9 Ω cm 2 Compared to the highly stable superhydrophobic composite material with a flexible armor structure used for metal corrosion protection in Example 1 (R... ct =9.53×10 10 Ω cm 2 The electrochemical performance was reduced by one order of magnitude, and the corrosion resistance was significantly reduced.

[0169] As can be seen from the test results of Comparative Example 6, due to the excessively small size of the flexible armor structure, the mechanical wear resistance of the coating is significantly reduced, and the corrosion resistance is also decreased. However, by introducing a flexible armor structure of appropriate size, the mechanical wear resistance and corrosion resistance of the composite material coating are significantly improved.

[0170] Comparative Example 7

[0171] 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. After continuous stirring at room temperature for 12 h (this process is to modify the superhydrophilic metal-based nano aluminum oxide particles through the hydrolysis and condensation reaction of fluorosilane), dry the resulting suspension to obtain superhydrophobic nano aluminum oxide particles.

[0172] 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-alumina particles and stir magnetically for 3 h to uniformly disperse the superhydrophobic nano-alumina 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 superhydrophobic suspension with a surface layer was successfully prepared.

[0173] 3. A diluted solution of adhesive E44 and curing agent polyamide (mass ratio of E44 to polyamide 1:1) was prepared using anhydrous ethanol as the diluent. The diluted solution was sprayed onto the surface of a Q235 carbon steel substrate under a pressure of 0.3 MPa to prepare an adhesive layer. Then, 40-50 mesh recycled rubber granules from waste tires were uniformly bonded to the surface (rubber granule dosage 268 g / m²). 2 Once it has fully solidified, a flexible armor structure is constructed.

[0174] 4. Apply the superhydrophobic suspension prepared in step 2 to the surface of the flexible armor structure prepared in step 3 using a spray gun (spraying pressure: 0.3 MPa, spraying distance: 15 cm, suspension volume: 1.0 mL / cm). 2 After complete curing, a control coating sample was obtained.

[0175] The performance testing method for the comparative coating sample obtained in Comparative Example 7 is the same as that in Example 1, and the test results are as follows:

[0176] 1. Coating wetting properties: Water droplets were placed on the coating surface and measured using a contact angle meter. The water contact angle of the coating surface was 156.7° and the roll-off angle was 5.1°. This shows that the prepared coating has excellent superhydrophobic properties.

[0177] 2. Mechanical stability test of coating: (1) After 120 wear cycles under a 100 g load of 2000 grit sandpaper, the water droplet contact angle of the coating is less than 150° and the roll-off angle is greater than 10°. It can be seen that the prepared superhydrophobic surface coating loses its superhydrophobic properties after a certain degree of wear and has poor mechanical wear resistance. (2) After 65 peel cycles of 3M tape, the water droplet contact angle of the coating is less than 150° and the roll-off angle is greater than 10°. It can be seen that the prepared superhydrophobic surface coating loses its superhydrophobic properties after a certain degree of tape peel and has poor adhesion between the coating and the substrate.

[0178] 3. Coating corrosion resistance test - electrochemical impedance spectroscopy test: The results show that the charge transfer resistance R of the coating ct =4.85×10 9 Ω cm 2Compared to the highly stable superhydrophobic composite material with a flexible armor structure used for metal corrosion protection in Example 1 (R... ct =9.53×10 10 Ω cm 2 The electrochemical performance was reduced by one order of magnitude, and the corrosion resistance was significantly reduced.

[0179] As can be seen from the test results of Comparative Example 7, due to the excessive size of the flexible armor structure, the mechanical wear resistance of the coating is significantly reduced, and the corrosion resistance is also reduced. However, by introducing a flexible armor structure of appropriate size, the mechanical wear resistance and corrosion resistance of the composite material coating are significantly improved.

[0180] Comparative Example 8

[0181] 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. After continuous stirring at room temperature for 12 h (this process is to modify the superhydrophilic metal-based nano aluminum oxide particles through the hydrolysis and condensation reaction of fluorosilane), dry the resulting suspension to obtain superhydrophobic nano aluminum oxide particles.

[0182] 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-alumina particles and stir magnetically for 3 h to uniformly disperse the superhydrophobic nano-alumina 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 superhydrophobic suspension with a surface layer was successfully prepared.

[0183] 3. A diluted solution of adhesive E44 and curing agent polyamide (mass ratio of E44 to polyamide 1:1) was prepared using anhydrous ethanol as the diluent. The diluted solution was sprayed onto the surface of a Q235 carbon steel substrate under a pressure of 0.3 MPa to prepare an adhesive layer. Then, 60-65 mesh recycled rubber granules from waste tires were uniformly bonded to the surface (rubber granule dosage 268 g / m²). 2 Once it has fully solidified, a flexible armor structure is constructed.

[0184] 4. Apply the superhydrophobic suspension prepared in step 2 to the surface of the flexible armor structure prepared in step 3 using a spray gun (spraying pressure: 0.3 MPa, spraying distance: 15 cm, suspension volume: 0.1 mL / cm). 2 After complete curing, a control coating sample was obtained.

[0185] The performance testing method for the comparative coating sample obtained in Comparative Example 8 is the same as that in Example 1, and the test results are as follows:

[0186] Coating wetting properties: Water droplets were placed on the coating surface and measured using a contact angle meter. The water contact angle of the coating surface was 139.2°, indicating that the prepared control coating sample did not have superhydrophobic properties.

[0187] The test results of Comparative Example 8 show that the amount of suspension used has a certain impact on the superhydrophobic performance of the coating. If the amount is too small, the coating will not be able to achieve superhydrophobic performance.

Claims

1. A method for preparing a highly stable superhydrophobic composite material with a flexible armor structure for metal corrosion protection, characterized in that, Includes the following steps: S1. Preparation of superhydrophobic modified nanoparticles: Hydrophilic nanoparticles were ultrasonically dispersed in an organic solvent, and then a low surface energy organosilane coupling agent was added under stirring conditions to obtain superhydrophobic modified nanoparticles; the volume ratio of the low surface energy organosilane coupling agent to the organic solvent was 0.05:3~0.15:3, and the mass concentration of the nanoparticles was 0.10~0.30 g / mL; the modification reaction conditions were room temperature and the reaction time was 6~24 h. S2. Preparation of superhydrophobic suspension by phase separation method: Polyester is completely dissolved in an organic solvent, and then superhydrophobic modified nanoparticles are added under stirring and stirred until completely dispersed. After the superhydrophobic nanoparticles are completely dispersed, a non-solvent is added to induce phase separation. After phase separation is completed, a superhydrophobic suspension is obtained. 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; the mass concentration of polyester is 0.01~0.10 g / mL; the non-solvent for non-solvent-induced phase separation is anhydrous ethanol, and the volume ratio of non-solvent to organic solvent is 0.10~0.20 mL / mL. S3. Preparation of the flexible armor structure: An epoxy resin adhesive is diluted in an organic solvent to prepare an epoxy diluent. This epoxy diluent is then sprayed onto the surface of a pre-treated metal substrate to form an epoxy adhesive layer. Flexible armor particles are then uniformly bonded to the surface of the epoxy adhesive layer. After curing, the flexible armor structure is obtained. The flexible armor particles are recycled rubber granules from waste tires, with a particle size of 60-65 mesh. The amount of flexible armor particles used is 100-300 g / m³. 2 ; S4. Preparation of a highly stable superhydrophobic composite material with a flexible armor structure for metal corrosion protection: The superhydrophobic suspension prepared in S2 is sprayed onto the surface of the flexible armor structure prepared in S3 using a spray gun. After complete curing, a highly stable superhydrophobic composite material with a flexible armor structure for metal corrosion protection is obtained.

2. The method for preparing a highly stable superhydrophobic composite material with a flexible armor structure for metal corrosion protection according to claim 1, characterized in that, In step S1, the nanoparticles are one or more of the following: nano-alumina particles, nano-silica particles, nano-titanium dioxide particles, and nano-zirconium dioxide particles; the low surface energy organosilane coupling agent is one or more of the following: 1H,1H,2H,2H-perfluorodecyltrimethoxysilane, 1H,1H,2H,2H-perfluorooctyltrimethoxysilane, or 1H,1H,2H,2H-perfluorodecyltriethoxysilane.

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

4. The method for preparing the highly stable superhydrophobic composite material with 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.

5. The method for preparing a highly stable superhydrophobic composite material with a flexible armor structure for metal corrosion protection according to claim 1, characterized in that, In step S3, the mass fraction of epoxy resin adhesive in the epoxy diluent is 20%~30%.

6. The method for preparing a highly stable superhydrophobic composite material with a flexible armor structure for metal corrosion protection according to claim 1, characterized in that, In step S4, the superhydrophobic suspension is sprayed onto the surface of the flexible armor structure using a spraying method, with a dosage of 0.60~1.20 mL / cm³. 2 .

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