A super wear-resistant and super hydrophobic fluorocarbon anti-corrosion coating, its preparation method and application

Abstract

This invention provides an ultra-wear-resistant and ultra-hydrophobic fluorocarbon anti-corrosion coating, its preparation method, and its application, belonging to the field of coatings. The preparation method of the fluorocarbon anti-corrosion coating disclosed in this invention includes the following steps: preparation of hydrophobically modified nanoparticles, preparation of hydrophobically loaded hybrid fillers, and preparation of the ultra-wear-resistant and ultra-hydrophobic coating. In this invention, hydrophobically modified nanoparticles are loaded into porous microshells to obtain hydrophobically loaded hybrid fillers, which are then uniformly dispersed in fluorocarbon resin to obtain an anti-corrosion coating with both ultra-hydrophobic and ultra-wear-resistant functions. Coatings made with this invention exhibit excellent non-adhesive properties and self-cleaning properties.

Description

Technical Field

[0001] This invention belongs to the field of coatings, specifically relating to an ultra-wear-resistant and ultra-hydrophobic fluorocarbon anti-corrosion coating, its preparation method, and its application. Background Technology

[0002] In many industrial sectors such as marine engineering, transportation, power facilities, and chemical machinery, metal structural components are exposed to harsh environments such as humidity, salt spray, and acid and alkali pollutants for a long time. Surface corrosion is the main reason for shortened service life and soaring maintenance costs.

[0003] Inspired by the lotus effect, superhydrophobic coatings offer a promising solution for achieving self-cleaning and active corrosion protection. By constructing a micro-nano composite rough structure and modifying it with low surface energy materials, the coating surface achieves a water contact angle exceeding 150° and a roll-off angle below 10°. This property endows the coating with excellent self-cleaning capabilities; rolling water droplets effectively carry away contaminants, keeping the surface clean. More importantly, the superhydrophobic state significantly hinders direct and continuous contact between water, oxygen, and corrosive ions and the coating surface, thus providing an active corrosion protection mechanism.

[0004] However, existing superhydrophobic coatings generally suffer from the fatal flaw of poor mechanical stability: their surface micro- and nano-structures are easily damaged by mechanical forces such as sandpaper abrasion, gravel impact, and scratching, leading to a rapid loss of superhydrophobic properties. In recent years, researchers have attempted to improve coating durability by introducing high-elasticity modulus matrices and self-healing materials, but these methods suffer from complex preparation processes, weakened hydrophobicity, or difficulty in large-scale application. Therefore, achieving both ultra-wear resistance and superhydrophobic self-cleaning function while ensuring long-term corrosion protection remains a significant technical challenge. Summary of the Invention

[0005] The purpose of this invention is to provide an ultra-wear-resistant and ultra-hydrophobic fluorocarbon anti-corrosion coating, its preparation method and application, which effectively overcomes the shortcomings of existing technologies such as poor mechanical durability of ultra-hydrophobic coatings and limited surface functions of fluorocarbon coatings.

[0006] To achieve the above or other objectives, the present invention is implemented through the following technical solutions.

[0007] A method for preparing an ultra-wear-resistant and ultra-hydrophobic fluorocarbon anti-corrosion coating includes the following steps: (1) Preparation of hydrophobic modified nanoparticles; (2) Preparation of hydrophobic loaded hybrid fillers; (3) Preparation of ultra-wear resistant and ultra-hydrophobic fluorocarbon anti-corrosion coatings.

[0008] Specifically, it includes the following steps: (1) Preparation of hydrophobic modified nanoparticles: Ammonia water was added to a mixed solvent of ethanol and deionized water to obtain an alkaline solution. Then, nanoparticles and modifiers were added, stirred evenly, and reacted under heating conditions to carry out surface modification. After the reaction was completed, the surface was treated to obtain hydrophobic modified nanoparticles. (2) Preparation of hydrophobic loaded hybrid filler: The porous microspheres were calcined at high temperature to remove impurities, and after cooling, they were dispersed in hydrogen peroxide solution for hydrophilic activation treatment. After the treatment, they were washed with deionized water until neutral and dried to obtain an activated shell. Then, the hydrophobic modified nanoparticles prepared in step (1) were mixed with the activated shell, an organic solvent was added, and the mixture was stirred, filtered, washed, and dried to obtain the loaded hybrid filler. The loaded hybrid filler and the hydrophobic modifier were mixed in a mixed solvent of ethanol and water, and the solution was adjusted to weak alkalinity with ammonia water. After heating and reaction, the hydrophobic loaded hybrid filler was obtained. (3) Preparation of super wear-resistant and super hydrophobic fluorocarbon anti-corrosion coating: The hydrophobic loaded hybrid filler obtained in step (2) is dispersed in propylene glycol methyl ether acetate solvent and stirred until uniformly dispersed to obtain a hydrophobic loaded hybrid filler dispersion. Then, the hydrophobic loaded hybrid filler dispersion is added to fluorocarbon varnish and stirred to obtain a super wear-resistant and super hydrophobic fluorocarbon anti-corrosion coating.

[0009] Furthermore, in step (1), the volume ratio of ethanol to deionized water in the mixed solvent is (80~100):5.

[0010] Furthermore, in step (1), the volume ratio of ammonia to ethanol is (0.5~1.0):100.

[0011] Further, in step (1), the nanoparticles are selected from one or more of silicon dioxide, titanium dioxide, and aluminum oxide. Preferably, the particle size range of the nanoparticles is 10~100 nm.

[0012] Furthermore, in step (1), the mass ratio of nanoparticles to mixed solvent is (5~20):100.

[0013] Furthermore, in step (1), the modifier is selected from one or more of nonafluorohexyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, and heptadecafluorodecyltrimethoxysilane.

[0014] Furthermore, in step (1), the mass ratio of the modifier to the nanoparticles is (4~12):100.

[0015] Furthermore, in step (1), the heating temperature is 40~60℃ and the reaction time is 6~12 h.

[0016] Furthermore, the processing after the reaction in step (1) includes, but is not limited to, centrifugation, washing, filtration, and drying. Preferably, the drying temperature is 50~80℃ and the drying time is 12~24 h.

[0017] Further, in step (2), the porous microspheres are selected from one or more of diatomaceous earth, porous silica, and zeolite. Preferably, the porous microspheres have a particle size range of 5~50 μm and a pore size of 50~600 nm.

[0018] Furthermore, in step (2), the high-temperature calcination temperature is 400~600℃ and the calcination time is 1~3 h.

[0019] Furthermore, in step (2), the mass ratio of porous microspheres to hydrogen peroxide solution is (4~22):100.

[0020] Furthermore, the mass fraction of the hydrogen peroxide solution in step (2) is 20%~60%.

[0021] Furthermore, in step (2), the reaction temperature for hydrophilic activation treatment is 100~120℃, and the reaction time is 12~24h.

[0022] Furthermore, in step (2), the mass ratio of hydrophobic modified nanoparticles to activated shell is (20~40):100.

[0023] Furthermore, in step (2), the mass ratio of the activated shell to the organic solvent is (5~15):100.

[0024] Furthermore, in step (2), the organic solvent is selected from butyl acetate and propylene glycol methyl ether acetate.

[0025] Furthermore, in step (2), the hydrophobic modified nanoparticles are mixed and stirred with the activated shell for 2 to 4 hours to allow the hydrophobic modified nanoparticles to fully enter the pores of the activated shell.

[0026] Furthermore, in step (2), the hydrophobic modifier is selected from one or more of n-octyltriethoxysilane, nonafluorohexyltriethoxysilane, tridecafluorooctyltriethoxysilane, and heptadecafluorodecyltriethoxysilane.

[0027] Furthermore, in step (2), the mass ratio of the hydrophobic modifier to the loaded hybrid filler is (5~20):100.

[0028] Furthermore, in step (2), the reaction temperature of the heating reaction is 40~60℃ and the reaction time is 6~12 h.

[0029] Further, in step (2), the volume ratio of ethanol to water in the mixed solvent of ethanol and water is (80~100):5. Preferably, the mass ratio of the loaded hybrid filler to the mixed solvent is (5~20):100.

[0030] Furthermore, in step (3), the mass ratio of the hydrophobic loaded hybrid filler to propylene glycol methyl ether acetate is (10~20):100.

[0031] Furthermore, in step (3), the stirring speed is 1000~2000 rpm and the stirring time is 0.5~2 h.

[0032] Furthermore, in step (3), the mass ratio of the hydrophobic loaded hybrid filler dispersion to the fluorocarbon varnish is (1.5~3.0):1.

[0033] The present invention also discloses an ultra-wear-resistant and ultra-hydrophobic fluorocarbon anti-corrosion coating prepared by the above method.

[0034] The present invention also protects an ultra-wear-resistant and ultra-hydrophobic fluorocarbon anti-corrosion coating comprising the above-mentioned ultra-wear-resistant and ultra-hydrophobic fluorocarbon anti-corrosion coating.

[0035] The preparation method of the super wear-resistant and super hydrophobic fluorocarbon anti-corrosion coating includes the following steps: mixing and stirring the super wear-resistant and super hydrophobic fluorocarbon anti-corrosion coating and curing agent evenly, coating it on the surface of the substrate, and curing it to obtain the super wear-resistant and super hydrophobic fluorocarbon anti-corrosion coating.

[0036] Preferably, the curing agent is selected from one of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.

[0037] Preferably, the mass ratio of the curing agent to the ultra-wear-resistant and ultra-hydrophobic fluorocarbon anti-corrosion coating is 1:(25~40).

[0038] Preferably, the curing temperature is 10~70℃ and the curing time is 12~72 h.

[0039] Preferably, the coating amount is 5~6 μm. 2 / kg.

[0040] Preferably, the substrate for coating is selected from stainless steel substrates. The coating method can be selected from conventional methods in the art, such as roller coating or spray coating.

[0041] This invention also protects the applications of the aforementioned ultra-wear-resistant and super-hydrophobic fluorocarbon waterproof materials in marine engineering, land and rail transportation, and chemical equipment.

[0042] In this invention, hydrophobically modified nanoparticles are first loaded into rigid inorganic porous microshells to construct a core-shell hybrid filler. The covalent bond density on the surface of the diatomaceous earth microshells is precisely controlled to form strong chemical bonds with the fluorocarbon resin matrix, thereby protecting the internal nanoseeds while withstanding mechanical wear. These cellular composite particles are then uniformly dispersed in fluorocarbon resin to prepare an anti-corrosion coating with both superhydrophobic and ultra-wear-resistant properties. When the coating is applied, the nanoseeds released from the porous shells instantly replenish the surface roughness and hydrophobicity upon mechanical friction, achieving self-supplementing ultra-wear resistance. The composite coating successfully achieves a water contact angle of 151° and a roll-off angle of less than 7°, exhibiting excellent non-adhesive properties and self-cleaning characteristics. The synergistic effect of this microshell functional filler and the fluorocarbon matrix greatly enhances the coating's self-cleaning effect and wear resistance, ultimately demonstrating a long-lasting anti-corrosion effect. Attached Figure Description

[0043] Figure 1 The infrared spectra of the hydrophobically modified nano-SiO2 and nano-SiO2 prepared in Example 1 are shown.

[0044] Figure 2 Thermogravimetric curves of nano-Al2O3 and hydrophobically modified nano-Al2O3 prepared in Example 2.

[0045] Figure 3 The water contact angle and roll-off angle of the super wear-resistant and super hydrophobic fluorocarbon coating prepared in Example 3 are tested, where a is the water contact angle result and b is the roll-off angle test result.

[0046] Figure 4 The contact angle test results of the super wear-resistant and super hydrophobic fluorocarbon coating prepared in Example 4 on common liquids (cola, orange juice, milk, coffee).

[0047] Figure 5 Images showing the dynamic adhesion performance test of the super wear-resistant and superhydrophobic fluorocarbon coating prepared in Example 1.

[0048] Figure 6 The corrosion resistance test results of the pipe coated with the super wear-resistant and super hydrophobic fluorocarbon coating prepared in Example 4 under acidic conditions. Detailed Implementation

[0049] The following specific embodiments illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and various details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention. It should be noted that, unless otherwise specified, the following embodiments and features described therein can be combined with each other.

[0050] It should be noted that the illustrations provided in this embodiment are only schematic representations of the basic concept of the present invention. Therefore, the drawings only show the components related to the present invention and are not drawn according to the actual number, shape and size of the components in the actual implementation. In the actual implementation, the form, quantity and proportion of each component can be arbitrarily changed, and the layout of the components may also be more complex.

[0051] It should be noted that the terms such as "upper", "lower", "left", "right", "middle" and "one" used in this specification are only for clarity of description and are not intended to limit the scope of the invention. Changes or adjustments to their relative relationships, without substantially altering the technical content, should also be considered as part of the scope of the invention.

[0052] The technical solution of the present invention will be described in detail below through several specific embodiments. Unless otherwise stated, the raw materials and reagents used in the following embodiments are commercially available products, or can be prepared by conventional methods in the art. Unless otherwise specified, the detection methods used in the embodiments of the present invention are conventional detection methods in the industry.

[0053] Example 1 Preparation of hydrophobically modified nanoparticles: 0.6 mL of ammonia was added to a mixed solvent of 90 mL anhydrous ethanol and 5 mL deionized water to obtain an alkaline solution. Then, 5 g of nano-silica and 0.3 g of nonafluorohexyltrimethoxysilane were added to this solution, and the reaction was carried out at 40 °C for 12 h. After the reaction, the mixture was centrifuged, washed with ethanol, and finally vacuum dried at 55 °C for 15 h to obtain hydrophobically modified SiO2 nanoparticles.

[0054] Preparation of hydrophobic loaded hybrid filler: 10 g of diatomaceous earth was calcined in a muffle furnace at 450℃ for 1.5 h, cooled, and ultrasonically dispersed in 100 mL of hydrogen peroxide solution. The mixture was then heated under reflux in an oil bath at 105℃ for 15 h. After the reaction was complete, the mixture was washed with deionized water until neutral and dried to obtain activated diatomaceous earth. Subsequently, 2 g of hydrophobically modified silica was mixed with 8 g of activated diatomaceous earth and added to 65 g of butyl acetate. The dispersion was mechanically stirred for 3 h to allow the hydrophobically modified nanoparticles to fully penetrate the shell pores. After filtration, washing, and drying, the loaded hybrid filler was obtained. 5 g of the loaded hybrid filler and 0.5 g of n-octyltriethoxysilane were added to a mixed solvent of ethanol and water. The solution was adjusted to weak alkalinity with ammonia and reacted at 40℃ for 12 h. The mixture was then washed with ethanol and dried to obtain the hydrophobic loaded hybrid filler.

[0055] Preparation of super wear-resistant and super hydrophobic fluorocarbon anti-corrosion coating: 12 g of hydrophobic loaded hybrid filler was dispersed in 100 g of propylene glycol methyl ether acetate and mechanically stirred at 1200 rpm for 1.5 h. Then, 60 g of fluorocarbon varnish was added to the dispersion and stirred evenly to obtain the super wear-resistant and super hydrophobic fluorocarbon anti-corrosion coating.

[0056] Preparation of super wear-resistant and super hydrophobic fluorocarbon anti-corrosion coating: 6.0 g of curing agent was added to the above super wear-resistant and super hydrophobic fluorocarbon anti-corrosion coating, stirred evenly, and then coated on the surface of the substrate. The coating was cured at 50°C for 48 h to obtain the super wear-resistant and super hydrophobic fluorocarbon anti-corrosion coating.

[0057] Example 2 Preparation of hydrophobically modified nanoparticles: 0.8 mL of ammonia was added to a mixed solvent of 85 mL anhydrous ethanol and 5 mL deionized water to obtain an alkaline solution. Then, 10 g of nano-alumina and 0.9 g of tridecafluorooctyltrimethoxysilane were added to this solution, and the reaction was carried out at 50 °C for 9 h. After the reaction, the nanoparticles were centrifuged, washed with ethanol, and finally vacuum dried at 70 °C for 12 h to obtain the hydrophobically modified nanoparticles.

[0058] Preparation of hydrophobic loaded hybrid filler: 15 g of porous silica was calcined in a muffle furnace at 500℃ for 2.0 h. After cooling, it was ultrasonically dispersed in 120 mL of hydrogen peroxide solution and heated under reflux in an oil bath at 110℃ for 12 h. After the reaction was completed, it was washed with deionized water until neutral and dried to obtain activated porous silica. Subsequently, 3 g of hydrophobic modified alumina and 10 g of activated diatomaceous earth were mixed and added to 80 g of propylene glycol methyl ether acetate. The dispersion was mechanically stirred for 3.5 h to allow the hydrophobic modified nanoparticles to fully enter the shell pores. After filtration, washing, and drying, the loaded hybrid filler was obtained. 10 g of the loaded hybrid filler and 1.5 g of nonafluorohexyltriethoxysilane were added to a mixed solvent of ethanol and water. The solution was adjusted to weak alkalinity with ammonia and reacted at 50℃ for 10 h. Then, it was washed with ethanol and dried to obtain the hydrophobic loaded hybrid filler.

[0059] Preparation of super wear-resistant and super hydrophobic fluorocarbon anti-corrosion coating: 4 g of hydrophobic loaded hybrid filler was dispersed in 30 g of propylene glycol methyl ether acetate and mechanically stirred at 1000 rpm for 1.5 h. Then, 15 g of fluorocarbon varnish was added to the dispersion and stirred evenly to obtain the super wear-resistant and super hydrophobic fluorocarbon anti-corrosion coating.

[0060] Preparation of super wear-resistant and super hydrophobic fluorocarbon anti-corrosion coating: Take 1.5 g of curing agent and add it to the super wear-resistant and super hydrophobic fluorocarbon anti-corrosion coating. After stirring evenly, apply it to the surface of the substrate and cure it at 60℃ for 36 h to obtain the super wear-resistant and super hydrophobic fluorocarbon anti-corrosion coating.

[0061] Example 3 Preparation of hydrophobically modified nanoparticles: 1.0 mL of ammonia was added to a mixed solvent of 100 mL anhydrous ethanol and 5 mL deionized water to obtain an alkaline solution. Then, 15 g of nano-titanium dioxide and 1.5 g of heptadecafluorodecyltrimethoxysilane were added to this solution, and the reaction was carried out at 60 °C for 6 h. After the reaction, the nanoparticles were centrifuged, washed with ethanol, and finally vacuum dried at 75 °C for 12 h to obtain the hydrophobically modified nanoparticles.

[0062] Preparation of hydrophobic loaded hybrid filler: 15 g of zeolite was calcined in a muffle furnace at 550℃ for 1.5 h, cooled, and ultrasonically dispersed in 150 mL of hydrogen peroxide solution. The mixture was then heated under reflux in an oil bath at 110℃ for 15 h. After the reaction was complete, the mixture was washed with deionized water until neutral and dried to obtain activated porous silica. Subsequently, 3 g of hydrophobically modified titanium dioxide and 9 g of activated diatomaceous earth were mixed and added to 90 g of butyl acetate. The dispersion was mechanically stirred for 4.0 h to allow the hydrophobically modified nanoparticles to fully enter the shell pores. After filtration, washing, and drying, the loaded hybrid filler was obtained. 8 g of the loaded hybrid filler and 1.2 g of tridecafluorooctyltriethoxysilane were added to a mixed solvent of ethanol and water. The solution was adjusted to weak alkalinity with ammonia and reacted at 60℃ for 8 h. The mixture was then washed with ethanol and dried to obtain the hydrophobic loaded hybrid filler.

[0063] Preparation of super wear-resistant and super hydrophobic fluorocarbon anti-corrosion coating: 3 g of hydrophobic loaded hybrid filler was dispersed in 25 g of propylene glycol methyl ether acetate and mechanically stirred at 1500 rpm for 1.0 h. Then, 12 g of fluorocarbon varnish was added to the dispersion and stirred evenly to obtain the super wear-resistant and super hydrophobic fluorocarbon anti-corrosion coating.

[0064] Preparation of super wear-resistant and super hydrophobic fluorocarbon anti-corrosion coating: 1.2 g of curing agent was added to the above super wear-resistant and super hydrophobic fluorocarbon anti-corrosion coating, stirred evenly, and then coated on the surface of the substrate. The coating was cured at 70°C for 12 h to obtain the super wear-resistant and super hydrophobic fluorocarbon anti-corrosion coating.

[0065] Example 4 Preparation of hydrophobically modified nanoparticles: 0.7 mL of ammonia was added to a mixed solvent of 95 mL anhydrous ethanol and 5.5 mL deionized water to obtain an alkaline solution. Then, 8 g of nano-silica and 0.8 g of heptadecafluorodecyltrimethoxysilane were added to this solution, and the reaction was carried out at 55 °C for 9 h. After the reaction, the nanoparticles were centrifuged, washed with ethanol, and finally vacuum dried at 80 °C for 12 h to obtain the hydrophobically modified nanoparticles.

[0066] Preparation of hydrophobic loaded hybrid filler: 12 g of diatomaceous earth was calcined in a muffle furnace at 550℃ for 2.5 h. After cooling, it was ultrasonically dispersed in 100 mL of hydrogen peroxide solution and heated under reflux in an oil bath at 105℃ for 15 h. After the reaction was completed, it was washed with deionized water until neutral and dried to obtain activated porous silica. Subsequently, 2.5 g of hydrophobic modified silica was mixed with 8.5 g of activated diatomaceous earth and added to 100 g of propylene glycol methyl ether acetate. The dispersion was mechanically stirred for 3.0 h to allow the hydrophobic modified nanoparticles to fully enter the shell pores. After filtration, washing, and drying, the loaded hybrid filler was obtained. 12 g of the loaded hybrid filler and 1.0 g of heptadecafluorodecyltriethoxysilane were added to a mixed solvent of ethanol and water. The solution was adjusted to weak alkalinity with ammonia and reacted at 60℃ for 7 h. Then, it was washed with ethanol and dried to obtain the hydrophobic loaded hybrid filler.

[0067] Preparation of super wear-resistant and super hydrophobic fluorocarbon anti-corrosion coating: 10 g of hydrophobic loaded hybrid filler was dispersed in 70 g of propylene glycol methyl ether acetate and mechanically stirred at 1800 rpm for 0.5 h. Then, 45 g of fluorocarbon varnish was added to the dispersion and stirred evenly to obtain the super wear-resistant and super hydrophobic fluorocarbon anti-corrosion coating.

[0068] Preparation of super wear-resistant and super hydrophobic fluorocarbon anti-corrosion coating: Take 4.5 g of curing agent and add it to the above super wear-resistant and super hydrophobic fluorocarbon anti-corrosion coating. After stirring evenly, apply it to the surface of the substrate and cure it at 50℃ for 40 h to obtain the super wear-resistant and super hydrophobic fluorocarbon anti-corrosion coating.

[0069] Comparative Example 1 Preparation of hydrophobically modified nanoparticles: The preparation method is the same as in Example 1; 12 g of hydrophobically modified nanoparticles were dispersed in 100 g of propylene glycol methyl ether acetate and mechanically stirred at 1200 rpm for 1.5 h. Then, 60 g of fluorocarbon varnish was added to the dispersion and stirred until homogeneous to obtain the coating.

[0070] Add 6.0 g of curing agent to the above coating, stir evenly, apply to the surface of the substrate, and cure at 50°C for 48 hours to obtain the coating.

[0071] Comparative Example 2 Preparation of hydrophobic modified nanoparticles: same as the preparation method in Example 2.

[0072] Preparation of the supported hybrid filler: same as the preparation method in Example 2.

[0073] 4 g of loaded hybrid filler was dispersed in 30 g of propylene glycol methyl ether acetate and mechanically stirred at 1000 rpm for 1.5 h. Then, 15 g of fluorocarbon varnish was added to the dispersion and stirred evenly to obtain the fluorocarbon anti-corrosion coating.

[0074] Add 1.5 g of curing agent to the fluorocarbon anti-corrosion coating, stir evenly, and then coat it on the surface of the substrate. Cur it at 60℃ for 36 h to obtain the fluorocarbon anti-corrosion coating.

[0075] Performance Characterization 1. To verify the successful preparation of hydrophobically modified nanoparticles and the chemical structure of the cellular composite particles, infrared spectroscopy was performed on unmodified nano-SiO2 and the hydrophobically modified nano-SiO2 prepared in Example 1. The test results are as follows: Figure 1 As shown in the figure. It can be seen from the figure that unmodified nano-SiO2 at 3430 cm⁻¹... -1 A distinct -OH stretching vibration peak is observed at 1100 cm⁻¹. -1 The peak at 1200 cm⁻¹ represents the antisymmetric stretching vibration of Si-O-Si; while the hydrophobic modified SiO₂ nanoparticles obtained by modification with nonafluorohexyltrimethoxysilane, although at 1200 cm⁻¹... -1 A characteristic absorption peak of the CF bond appears at 2980 cm⁻¹, but this peak is masked by the antisymmetric stretching vibration peak of Si-O-Si. The weakening of the -OH stretching vibration peak indicates that some hydroxyl groups on the particle surface have been substituted. -1 and 2890 cm -1 The presence of asymmetric stretching vibration peaks of -CH3 and -CH2 at the respective locations indicates that the fluorinated silane coupling agent has been successfully grafted onto the nano-SiO2 surface, which in turn helps to improve the hydrophobicity of the coating.

[0076] 2. Thermogravimetric analysis (TGA) tests were performed on the unmodified nano-Al2O3 and the hydrophobically modified nano-Al2O3 prepared in Example 2, respectively. The obtained TGA curves are shown below. Figure 2 As shown in the figure, unmodified nano-Al2O3 experiences a mass loss of approximately 1.2% before 200℃, mainly due to the desorption of adsorbed water. Between 200 and 700℃, the mass loss is approximately 1.1%, attributed to the decomposition of surface hydroxyl groups. In contrast, hydrophobically modified nano-Al2O3 exhibits a more significant weight loss (approximately 5%) between 30 and 700℃, corresponding to the decomposition of the grafted fluorinated silane chains, indicating successful grafting of a hydrophobic silane coupling agent onto the surface of nano-Al2O3.

[0077] 3. To investigate the superhydrophobic properties of the coating, the superabrasion-resistant and superhydrophobic fluorocarbon coating prepared in Example 3 was subjected to water contact angle and roll-off angle tests. The water droplet volume used for measuring the water contact angle and roll-off angle was 5 μL. The water droplet was placed on the surface of the superabrasion-resistant and superhydrophobic fluorocarbon coating. After stabilization, the droplet profile was captured using the instrument's built-in camera, and the contact angle was calculated. Five different locations were tested for each sample, and the average value was taken. The roll-off angle test used the tilting plate method. The superabrasion-resistant and superhydrophobic fluorocarbon coating sample was horizontally fixed on a tiltable sample stage. After the water droplet was placed on the coating surface, the sample stage was slowly tilted, and the tilt angle at which the droplet began to roll was recorded. Five tests were performed for each sample, and the average value was taken. The test results are as follows: Figure 3 As shown, the static water contact angle of the super wear-resistant and superhydrophobic fluorocarbon coating in Example 3 reached 153.5° and the roll-off angle was 6.8°, demonstrating excellent superhydrophobic properties.

[0078] 4. To investigate the wetting performance of the coating on different liquids, the ultra-wear-resistant and superhydrophobic fluorocarbon coating prepared in Example 4 was used to test its contact angles with common liquids such as cola, orange juice, milk, and coffee. The testing method was the same as that for the water contact angle test described above. The results are as follows: Figure 4 As shown, from Figure 4 It can be seen that the contact angles of cola, milk, coffee, and orange juice are 152.7°, 150.3°, 150.8°, and 151.4°, respectively, all of which maintain excellent superhydrophobic properties.

[0079] 5. To verify the ultra-wear-resistant performance of the coating, the coatings prepared in Example 1, Comparative Example 1, and Comparative Example 2 were subjected to wear resistance tests. The test method was as follows: 400-grit sandpaper was fixed on the bottom surface of a 1 kg load, with the front of the sandpaper in direct contact with the coating surface. Then, the load was driven to move back and forth to perform friction and wear. After every 100 wear cycles, the tested coating sample was removed, and the surface dust was blown away with compressed air. Then, the contact angle was tested. The test results are shown in Table 1. The results show that the initial contact angle of the coating in Example 1 was 152.7°, and after 1000 wear cycles, its water contact angle remained at 152.3°. The initial water contact angle of the coating in Comparative Example 1 was only 132.5°, which dropped to 98.6° after 200 wear cycles; the initial water contact angle of the coating in Example 2 (unhydrophobic modified load hybrid filler) was 140.2°, which dropped to 112.3° after 200 wear cycles. The above results indicate that the coating containing hydrophobic loaded hybrid filler prepared in this invention has excellent wear resistance, and the protection of the internal nanoseeds by the porous microshell and the release and replenishment of the nanoseeds after wear are the main reasons for maintaining the superhydrophobicity.

[0080] Table 1. Water contact angles of various coatings after different wear cycles. 6. To verify the non-adhesiveness of the coating to water droplets, a dynamic water droplet adhesion experiment was conducted on the ultra-wear-resistant and superhydrophobic fluorocarbon coating prepared in Example 1. A high-speed camera was used to record the entire process of the syringe dropper contacting, squeezing, lifting, and detaching from the coating surface. The results are as follows: Figure 5 As shown, when the syringe dropper slowly approaches the coating surface, the water droplet is compressed and deformed; when the syringe is lifted, the water droplet completely leaves the coating surface, and there is no water residue left on the syringe needle tip, indicating that the coating has extremely low adhesion to water droplets. Combined with the coating's low roll-off angle, this confirms that the coating has ultra-low adhesion characteristics.

[0081] 7. To investigate the corrosion resistance of the coating, the ultra-wear-resistant and ultra-hydrophobic fluorocarbon coating obtained in Example 4 was applied to Q235 carbon steel pipes. The coated pipes were then immersed in a 10 wt.% sulfuric acid solution. Samples were taken every two days to observe changes in the coating's appearance. The changes in appearance are as follows: Figure 6 As shown, the appearance of the coating did not change after 12 days of immersion. The surface coating exhibits good stability in an acidic environment. This is mainly due to the synergistic effect of the hydrophobic modification of the loaded hybrid filler, the micro-nano rough structure of the coating, and the low surface energy fluorocarbon resin, which enables the coating to effectively resist the erosion of acidic corrosive media.

[0082] Based on the above experiments and results, it can be seen that the coating obtained by applying the super-wear-resistant and superhydrophobic fluorocarbon coating to the substrate prepared in this invention can successfully achieve a water contact angle of up to 151° and a roll-off angle of less than 7°, exhibiting excellent non-adhesive properties and self-cleaning ability. Furthermore, in the coating preparation process of this invention, the synergistic effect of the microshell functional filler and the fluorocarbon matrix greatly enhances the coating's self-cleaning effect and wear resistance, ultimately demonstrating a long-lasting anti-corrosion effect, and thus possessing greater application value in the fields of corrosion prevention, self-cleaning, and wear resistance.

[0083] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by those skilled in the art without departing from the spirit and technical concept disclosed in the present invention should still be covered by the claims of the present invention.

Claims

1. A method for preparing an ultra-wear-resistant and ultra-hydrophobic fluorocarbon anti-corrosion coating, characterized in that, Includes the following steps: (1) Preparation of hydrophobic modified nanoparticles; (2) Preparation of hydrophobic loaded hybrid fillers; (3) Preparation of ultra-wear resistant and ultra-hydrophobic fluorocarbon anti-corrosion coatings.

2. The preparation method according to claim 1, characterized in that, The steps include: (1) Preparation of hydrophobic modified nanoparticles: Add ammonia to a mixed solvent of ethanol and deionized water to obtain an alkaline solution, then add nanoparticles and modifiers, stir evenly and react under heating conditions to carry out surface modification, and after the reaction is completed, process to obtain hydrophobic modified nanoparticles. (2) Preparation of hydrophobic loaded hybrid filler: porous microspheres were calcined at high temperature to remove impurities, and after cooling, they were dispersed in hydrogen peroxide solution for hydrophilic activation treatment. After the treatment, they were washed with deionized water until neutral and dried to obtain the activated shell layer. The hydrophobic modified nanoparticles prepared in step (1) are then mixed with the activated shell, an organic solvent is added, and the mixture is stirred, filtered, washed, and dried to obtain the loaded hybrid filler. The loaded hybrid filler is then mixed with the hydrophobic modifier in a mixed solvent of ethanol and water, the solution is adjusted to a weakly alkaline state with ammonia, and the reaction is heated to obtain the hydrophobic loaded hybrid filler. (3) Preparation of super wear-resistant and super hydrophobic fluorocarbon anti-corrosion coating: The hydrophobic loaded hybrid filler obtained in step (2) is dispersed in propylene glycol methyl ether acetate solvent and stirred until uniformly dispersed to obtain a hydrophobic loaded hybrid filler dispersion. Then, the hydrophobic loaded hybrid filler dispersion is added to fluorocarbon varnish and stirred to obtain a super wear-resistant and super hydrophobic fluorocarbon anti-corrosion coating.

3. The preparation method according to claim 2, characterized in that, Includes one or more of the following technical features: In step (1), the volume ratio of ethanol to deionized water in the mixed solvent is (80~100):

5. In step (1), the volume ratio of ammonia to ethanol is (0.5~1.0):100; In step (1), the nanoparticles are selected from one or more of silicon dioxide, titanium dioxide, and aluminum oxide; In step (1), the modifier is selected from one or more of nonafluorohexyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, and heptadecafluorodecyltrimethoxysilane; In step (1), the mass ratio of the modifier to the nanoparticles is (4~12):100; In step (1), the heating temperature is 40~60℃ and the reaction time is 6~12 h.

4. The preparation method according to claim 2, characterized in that, Includes one or more of the following technical features: In step (2), the porous microspheres are selected from one or more of diatomaceous earth, porous silica, and zeolite; In step (2), the high-temperature calcination temperature is 400~600℃ and the calcination time is 1~3 h; The reaction temperature for hydrophilic activation treatment in step (2) is 100~120℃, and the reaction time is 12~24 h; In step (2), the mass ratio of hydrophobic modified nanoparticles to activated shell is (20~40):100; In step (2), the organic solvent is selected from butyl acetate and propylene glycol methyl ether acetate.

5. The preparation method according to claim 2, characterized in that, Includes one or more of the following technical features: In step (2), the hydrophobic modifier is selected from one or more of n-octyltriethoxysilane, nonafluorohexyltriethoxysilane, tridecafluorooctyltriethoxysilane, and heptadecafluorodecyltriethoxysilane; In step (2), the mass ratio of the hydrophobic modifier to the supported hybrid filler is (5~20):100; In step (2), the heating reaction temperature is 40~60℃ and the reaction time is 6~12 h.

6. The preparation method according to claim 2, characterized in that, Includes one or more of the following technical features: In step (3), the mass ratio of the hydrophobic loaded hybrid filler to propylene glycol methyl ether acetate is (10~20):100; In step (3), the mass ratio of the hydrophobic loaded hybrid filler dispersion to the fluorocarbon varnish is (1.5~3.0):

1.

7. A super wear-resistant and super hydrophobic fluorocarbon anti-corrosion coating prepared by the preparation method according to any one of claims 1 to 6.

8. A super wear-resistant and super hydrophobic fluorocarbon anti-corrosion coating, characterized in that, Including the ultra-wear-resistant and ultra-hydrophobic fluorocarbon anti-corrosion coating as described in claim 7.

9. A method for preparing the ultra-wear-resistant and ultra-hydrophobic fluorocarbon anti-corrosion coating of claim 8, characterized in that, Includes the following steps: The ultra-wear-resistant and ultra-hydrophobic fluorocarbon anti-corrosion coating is mixed and stirred evenly with a curing agent, then applied to the surface of the substrate and cured to obtain the ultra-wear-resistant and ultra-hydrophobic fluorocarbon anti-corrosion coating.

10. The application of the ultra-wear-resistant and ultra-hydrophobic fluorocarbon anti-corrosion coating of claim 8 in marine engineering, land and rail transportation, and chemical equipment.

Images