Matrix with wear-resistant hydrophobic composite coating as well as preparation method and application of matrix

Abstract

The invention provides a matrix with a wear-resistant hydrophobic composite coating and a preparation method and application thereof, and the preparation method of the matrix with the wear-resistant hydrophobic composite coating comprises the following steps: cleaning or / and activating the surface of the matrix to obtain a pretreated matrix surface; mixing the dispersion liquid of the inorganic nanoparticles with adhesive resin to obtain a composite coating liquid; the composite coating liquid is formed on the surface of the pretreated substrate in a coating or dipping mode, and the substrate with a wet film on the surface is obtained; performing first heat treatment on the substrate with the wet film on the surface to obtain a substrate with a primary composite coating on the surface; and carrying out selective etching treatment on the adhesive resin in the primary composite coating. According to the preparation method of the matrix with the wear-resistant hydrophobic composite coating, a stable micro-nano coarse structure with inorganic nanoparticles as a framework is accurately constructed through surface selective etching, so that the coating has excellent wear resistance, hydrophobicity and corrosion resistance.

Description

Technical Field

[0001] This application relates to the field of materials surface engineering technology, and in particular to a substrate with a wear-resistant and hydrophobic composite coating, its preparation method and application. Background Technology

[0002] Hydrophobic coatings (water contact angle greater than 90°) have shown great application potential in fields such as anti-icing, anti-fogging, self-cleaning, metal corrosion protection, and oil-water separation. Currently, the mainstream method for constructing superhydrophobic surfaces is to combine low surface energy materials with micro- and nano-scale rough structures.

[0003] However, micro / nano rough structures that achieve superhydrophobicity often suffer from low mechanical strength and poor stability. In practical applications, even slight physical scratches or wear can easily damage these fine structures, leading to a sharp decline in hydrophobic properties or even permanent failure. While existing technologies attempt to enhance the mechanical properties of coatings by introducing inorganic nanoparticles (such as SiO2 and TiO2), they often face new challenges: on the one hand, high nanoparticle content leads to easy aggregation in polymer resins, making uniform dispersion difficult; on the other hand, the interfacial bonding between nanoparticles and the polymer matrix is ​​weak, making them prone to detachment from the matrix under stress, which can also lead to performance failure. Furthermore, many fabrication processes are complex and costly, or unsuitable for large-area, complex-shaped substrates, limiting their industrial application.

[0004] Therefore, developing a preparation method that is simple to process, has strong coating adhesion, long wear resistance and long service life, and can maintain stable superhydrophobic properties for a long time has become a technical problem that needs to be solved by those skilled in the art. Summary of the Invention

[0005] In view of this, one objective of this application is to overcome the shortcomings of the prior art and provide a method for preparing a substrate with a wear-resistant hydrophobic composite coating. This method aims to solve the technical problems of existing superhydrophobic coatings, such as poor mechanical wear resistance, vulnerability of micro / nano structures, weak adhesion to the substrate, and short service life.

[0006] Another objective of this application is to provide a substrate with a wear-resistant and hydrophobic composite coating, which is prepared by the method of this application for preparing a substrate with a wear-resistant and hydrophobic composite coating, and has high hardness, strong adhesion, excellent superhydrophobicity and durable wear resistance.

[0007] Another objective of this application relates to the application of a substrate having a wear-resistant and hydrophobic composite coating.

[0008] To achieve the above objectives, the first aspect of this application proposes a method for preparing a substrate with a wear-resistant and hydrophobic composite coating, comprising: The substrate surface is cleaned and / or activated to obtain a pretreated substrate surface; A composite coating solution is obtained by mixing a dispersion of inorganic nanoparticles with an adhesive resin. The composite coating liquid is formed on the surface of the pretreated substrate by coating or impregnation to obtain a substrate with a wet film on the surface; The substrate with a wet film on its surface is subjected to a first heat treatment to obtain a substrate with a primary composite coating on its surface. The adhesive resin in the primary composite coating is selectively etched to obtain the substrate with the wear-resistant and hydrophobic composite coating.

[0009] In some embodiments, the cleaning includes at least one of alkaline soaking, alkaline washing, water washing, alcohol washing, and airflow purging.

[0010] In some embodiments, the substrate surface activation treatment includes atmospheric pressure air plasma treatment.

[0011] In some embodiments, the surface energy of the adhesive resin is less than 50 mN / m.

[0012] In some embodiments, the intrinsic water contact angle of the adhesive resin is greater than 100°. In some embodiments, the adhesive resin includes at least one of silicone resin and fluorinated resin.

[0013] In some embodiments, the inorganic nanoparticles include at least one of carbon black, fumed silica, silicon carbide whiskers, carbon nanotubes, boron nitride nanosheets, and graphene.

[0014] In some embodiments, the volume equivalent particle size of the inorganic nanoparticles ranges from 20 to 500 nm.

[0015] In some embodiments, the inorganic nanoparticles are inorganic nanoparticles treated with a silane coupling agent.

[0016] In some embodiments, the mass ratio of the inorganic nanoparticles to the adhesive resin is (0.1-2):(9.9-38).

[0017] In some embodiments, the method for preparing the substrate with the wear-resistant and hydrophobic composite coating further includes: Inorganic nanoparticles are dispersed in an organic solvent to obtain a dispersion of the inorganic nanoparticles.

[0018] In some embodiments, the mass ratio of the inorganic nanoparticles to the organic solvent is (9.9-38):(60-90).

[0019] In some embodiments, the method for preparing the substrate with the wear-resistant and hydrophobic composite coating further includes: Before mixing the dispersion of inorganic nanoparticles with the adhesive resin, the inorganic nanoparticles in the dispersion of inorganic nanoparticles are surface-treated with a silane coupling agent.

[0020] In some embodiments, the selective etching process includes oxygen plasma etching.

[0021] In some embodiments, the process conditions for the selective etching process include: a plasma nozzle-substrate distance of 5-20 mm, a plasma output power of 450-1000 W, and an etching time of 5-60 min.

[0022] In some embodiments, the substrate is made of at least one of metal, polymer, ceramic, and glass.

[0023] In some embodiments, the coating method includes at least one of spraying, spin coating, and dipping.

[0024] In some embodiments, the thickness of the wet film is 10-500 μm.

[0025] In some embodiments, the first heat treatment is performed in an air atmosphere, the temperature of the first heat treatment is the curing temperature of the adhesive resin, and the time of the first heat treatment is 0.5-6 hours.

[0026] In some embodiments, the method for preparing the substrate with the wear-resistant hydrophobic composite coating further includes a second heat treatment step after the selective etching process.

[0027] In some embodiments, the process conditions for the second heat treatment include: 80-150°C in an air environment. o C Keep t h, 0 < t ≤2h.

[0028] The second aspect of this application discloses a substrate with a wear-resistant and hydrophobic composite coating, which is prepared using the preparation method of the substrate with a wear-resistant and hydrophobic composite coating described in the second aspect of this application.

[0029] In some embodiments, the substrate with the wear-resistant and hydrophobic composite coating includes the substrate and the wear-resistant and hydrophobic composite coating disposed on its surface; the wear-resistant and hydrophobic composite coating includes the adhesive resin and a plurality of the inorganic nanoparticles, and the adhesive resin and the plurality of the inorganic nanoparticles together constitute a micro-nano hierarchical rough structure.

[0030] In some embodiments, a portion of the inorganic nanoparticles are distributed in the bulk phase of the adhesive resin, while another portion is embedded in the surface layer of the adhesive resin and forms multiple protrusions on the surface of the adhesive resin.

[0031] In some embodiments, the number of inorganic nanoparticles distributed in the adhesive resin bulk phase is greater than the number of inorganic nanoparticles embedded in the adhesive resin surface layer.

[0032] In some embodiments, the substrate having the wear-resistant hydrophobic composite coating has at least one of the following characteristics: (1) The adhesion between the wear-resistant and hydrophobic composite coating and the substrate can be above 5.0 MPa; (2) The initial water contact angle of the wear-resistant hydrophobic composite coating can be above 150°; (3) The initial roll angle of the wear-resistant and hydrophobic composite coating can be below 10°; (4) Under the conditions of using CS-10 grinding wheel and 1000g load, the Taber wear resistance test was conducted, and the water contact angle of the wear-resistant hydrophobic composite coating decreased by less than 15% after 1000 revolutions; (5) The thickness of the wear-resistant and hydrophobic composite coating is 5-120 μm.

[0033] The third aspect of this application relates to the application of the substrate with wear-resistant and hydrophobic composite coating described in the second aspect of this application in the fields of anti-icing, anti-fogging, self-cleaning, metal corrosion protection, and oil-water separation.

[0034] The method for preparing a substrate with a wear-resistant and hydrophobic composite coating described in this application can bring at least the following beneficial effects: 1. Hydrophobic Durability: The surface etching process is not a simple modification, but rather a subtractive manufacturing process achieved through selective etching, precisely constructing a stable micro-nano rough structure with inorganic nanoparticles as the framework. The hard nanoparticles are firmly coated and fixed by the flexible resin, forming an internally reinforced composite structure. This structure can effectively disperse and buffer external stress, greatly improving the coating's scratch resistance and wear resistance.

[0035] 2. Strong coating adhesion: The low content of inorganic nanoparticles (not exceeding 5 wt.%) solves the problem of decreased mechanical strength of the coating due to excessive content. Through dual pretreatment of the substrate and nanoparticles, the interfacial bonding between the "substrate-resin-nanoparticles" is optimized, ensuring excellent adhesion of the coating on various substrates (such as metals, polymers, ceramics, and glass).

[0036] 3. Universality: This method has a simple process and is suitable for coating large-area and complex-shaped workpieces, and has good prospects for industrialization.

[0037] The substrate with wear-resistant and hydrophobic composite coating described in this application and its application both have at least the beneficial effects of the preparation method of the substrate with wear-resistant and hydrophobic composite coating described in this application.

[0038] Additional aspects and advantages of this application will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of this application. Attached Figure Description

[0039] The above and / or additional aspects and advantages of this application will become apparent and readily understood from the following description of the embodiments taken in conjunction with the accompanying drawings. in: Figure 1 This is a flowchart illustrating a method for preparing a substrate with a wear-resistant and hydrophobic composite coating, as shown in an exemplary embodiment of this application.

[0040] Figure 2 Comparison of surface scanning electron microscope (SEM) images of the hydrophobic composite coatings prepared in Example 1 and Comparative Example 2.

[0041] Figure 3 The graph shows a comparison of the water contact angle of the hydrophobic composite coatings prepared in Example 1 and Comparative Example 2 as a function of the number of rubbing cycles. Detailed Implementation

[0042] Embodiments of this application are described in detail below, with examples of these embodiments illustrated in the accompanying drawings. The embodiments described below with reference to the accompanying drawings are exemplary and intended to explain this application, and should not be construed as limiting it.

[0043] In this application, the disclosure of numerical ranges includes all values ​​throughout the range and the disclosure of further subdivisions of the range, including the endpoints and subranges given for these ranges.

[0044] Unless otherwise specified, all raw materials and equipment involved in this application are those that can be manufactured commercially or by known methods; and all methods involved are conventional methods unless otherwise specified.

[0045] When the term “and / or” is used in a list containing two or more items, it means that any of the listed items can be used alone or in combination with any one or more of the listed items. For example, the expression “A and / or B” is intended to mean A or B or A and B, that is, A only, B only, or a combination of A and B.

[0046] In this application, room temperature refers to 20-30°C.

[0047] <Preparation method of substrate with wear-resistant and hydrophobic composite coating> The following describes a method for preparing a substrate with a wear-resistant and hydrophobic composite coating according to an embodiment of this application, with reference to the accompanying drawings.

[0048] Figure 1 This is a flowchart illustrating a method for preparing a substrate with a wear-resistant and hydrophobic composite coating, as shown in an exemplary embodiment of this application.

[0049] like Figure 1 As shown, the method for preparing the substrate with the wear-resistant and hydrophobic composite coating includes the following steps: S101. Clean and / or activate the substrate surface to obtain a pretreated substrate surface.

[0050] In the embodiments of this application, the substrate surface is cleaned and / or activated to remove contaminants and / or modify the surface chemically, thereby improving the interfacial adhesion between the coating and the substrate.

[0051] In some embodiments, the material of the substrate includes, but is not limited to, at least one of metal, polymer, ceramic, glass, etc.

[0052] In some embodiments, the shape of the substrate includes, but is not limited to, standard shapes such as cuboids and cylinders, or other irregular shapes.

[0053] For example, the matrix includes, but is not limited to, at least one of glass fiber epoxy composite board, aluminum alloy board, glass board, etc.

[0054] It should be noted that, in the embodiments of this application, depending on the substrate material, one of three methods—cleaning, activation treatment, or cleaning and activation treatment—is selected for pretreatment. Specifically: When the substrate material is metal, ceramic, or glass, the pretreatment method is cleaning; When the substrate material is a polymer, the pretreatment method is cleaning and activation treatment.

[0055] In some embodiments, the cleaning includes at least one of alkaline soaking, alkaline washing, water washing, alcohol washing, and airflow purging.

[0056] In some embodiments, the activation treatment includes atmospheric pressure air plasma treatment.

[0057] S102. Mix the dispersion of inorganic nanoparticles with the adhesive resin to obtain a composite coating solution.

[0058] In some embodiments, the method for preparing the substrate with the wear-resistant and hydrophobic composite coating further includes: dispersing inorganic nanoparticles in an organic solvent to obtain a dispersion of the inorganic nanoparticles.

[0059] In some embodiments, the mass ratio of the inorganic nanoparticles to the organic solvent is (9.9-38):(60-90), including but not limited to 9.9:70, 9.9:80, 9.9:75, 24:60, 24:75, 24:90, 38:70, 38:75, or 38:80.

[0060] In some embodiments, the inorganic nanoparticles include, but are not limited to, at least one of carbon black, fumed silica, silicon carbide whiskers, carbon nanotubes, boron nitride nanosheets, and graphene.

[0061] In some embodiments, the volume equivalent particle size of the inorganic nanoparticles ranges from 20 to 500 nm, including but not limited to 50-450 nm, 100-400 nm, 150-350 nm, 200-300 nm, 20-400 nm, 20-300 nm, 20-200 nm, or 20-100 nm.

[0062] In some embodiments, the organic solvent includes, but is not limited to, at least one of ethyl acetate, xylene, etc.

[0063] In some embodiments, the method for preparing the substrate with the wear-resistant and hydrophobic composite coating further includes: Before mixing the dispersion of inorganic nanoparticles with the adhesive resin, the inorganic nanoparticles in the dispersion of inorganic nanoparticles are surface-treated with a silane coupling agent.

[0064] For example, the method of surface treatment of inorganic nanoparticles in the dispersion of inorganic nanoparticles with silane coupling agent is as follows: a certain amount of silane coupling agent (the mass of the silane coupling agent added is 1-5% of the mass of inorganic nanoparticles, such as 2%, 3% or 4%) is added to the dispersion of inorganic nanoparticles, and stirred at room temperature or heated (40-80℃, such as 50℃, 60℃ or 70℃) for 0.5-3h (for example, 1h or 2h).

[0065] For example, in the process of surface treatment of the inorganic nanoparticles in the dispersion of the inorganic nanoparticles with a silane coupling agent, the silane coupling agent used includes, but is not limited to, at least one of KH-560, KH-550, and A-151 silane coupling agents.

[0066] In the embodiments of this application, the inorganic nanoparticles in the dispersion of the inorganic nanoparticles are surface-treated with a silane coupling agent. The purpose is to introduce anchor points on the surface of the inorganic nanoparticles that can chemically or physically interact with the adhesive resin through the silane coupling agent, so as to enhance their bonding strength.

[0067] In some embodiments, the adhesive resin is a low surface energy adhesive resin with a surface energy of less than 50 mN / m, including but not limited to less than 40 mN / m, less than 30 mN / m, less than 20 mN / m or less than 10 mN / m, and optionally 20-25 mN / m.

[0068] In the embodiments of this application, a low surface energy adhesive resin is selected because it has strong hydrophobicity and an intrinsic water contact angle of over 100°, so that the final coating water contact angle can be controlled within the range of 100-170° through a subtractive process such as selective etching, depending on the application scenario.

[0069] In some embodiments, the adhesive resin includes, but is not limited to, at least one of silicone resin, fluorinated resin, etc.

[0070] For example, the silicone resin includes, but is not limited to, at least one of vulcanized silicone rubber, methyl silicone resin, phenyl silicone resin, etc., and may be selected as vulcanized silicone rubber.

[0071] For example, the fluorinated resin includes, but is not limited to, at least one of polytetrafluoroethylene, polyvinylidene fluoride, and (fluorinated ethylene / vinyl ether) alternating copolymer FEVE, and may be selected as (fluorinated ethylene / vinyl ether) alternating copolymer FEVE.

[0072] In some embodiments, the mass ratio of the inorganic nanoparticles to the adhesive resin is (0.1-2):(9.9-38), including but not limited to 0.1:15, 0.1:20, 0.1:25, 0.1:30, 1:15, 1:20, 1:25, 1:30, 1:35, 1:9.9, 1:38, 2:15, 2:20, 2:25, 2:30, or 2:35.

[0073] In the embodiments of this application, controlling the mass ratio of inorganic nanoparticles to binder resin within the above range can make the coating have better mechanical strength; excessive use of inorganic nanoparticles may lead to a decrease in the mechanical strength of the coating; excessive use of binder resin will affect the hydrophobic properties and stability of the micro-nano structure.

[0074] As an optional example, the composite coating liquid comprises the following components in parts by weight: 0.1-2 parts inorganic nanoparticles, 9.9-38 parts low surface energy adhesive resin, and 60-90 parts organic solvent.

[0075] It is understood that when the inorganic nanoparticles are not surface-treated, the inorganic nanoparticles in the above 0.1-2 parts of inorganic nanoparticles refer to the inorganic nanoparticles that have not been surface-treated; while when the inorganic nanoparticles are surface-treated inorganic nanoparticles, the inorganic nanoparticles in the above 0.1-2 parts of inorganic nanoparticles refer to the surface-treated inorganic nanoparticles.

[0076] In some embodiments, the method of mixing the dispersion of inorganic nanoparticles with the adhesive resin includes at least one of stirring, ultrasonic dispersion, etc., with stirring being the preferred method. The purpose is to form a composite coating liquid with uniform composition and good stability between the dispersion of inorganic nanoparticles and the adhesive resin.

[0077] S103. The composite coating liquid obtained in step S102 is applied to the surface of the pretreated substrate obtained in step S101 by coating or impregnation to obtain a substrate with a wet film on the surface.

[0078] In some embodiments, the coating method includes, but is not limited to, at least one of spraying, spin coating, etc.

[0079] In some embodiments, when the composite coating obtained in step S102 is formed on the pretreated substrate surface obtained in step S101 by immersion, the immersion process conditions include: immersion at room temperature and atmospheric pressure for 2-10 seconds.

[0080] In some embodiments, the thickness of the wet film is 50-100 μm.

[0081] S104. The substrate with a wet film on its surface obtained in step S103 is subjected to a first heat treatment to obtain a substrate with a primary composite coating on its surface.

[0082] In the embodiments of this application, the purpose of the first heat treatment is to achieve the evaporation of organic solvents in the wet film and the cross-linking and curing of the adhesive resin, while enabling the adhesive resin to form a robust primary composite coating through chemical bonding with the substrate surface and the surface of inorganic nanoparticles.

[0083] In some embodiments, the first heat treatment is performed in an air atmosphere, the temperature of the first heat treatment is the curing temperature of the adhesive resin, and the time of the first heat treatment is 0.5-6 hours.

[0084] For example, the duration of the first heat treatment includes, but is not limited to, 1 hour, 2 hours, 3 hours, 4 hours, or 5 hours.

[0085] It should be noted that different resins may have different curing temperatures, therefore the first heat treatment temperature may vary depending on the adhesive resin selected. For example, when the fluorinated resin is AGC's LF200 (fluorinated ethylene / vinyl ether) alternating copolymer FEVE, the first heat treatment temperature can be 120°C; while when the adhesive resin is Dow Chemical's 3145 vulcanized silicone rubber, the first heat treatment temperature can be 60°C; and so on.

[0086] S105. Selectively etch the adhesive resin in the substrate with the primary composite coating obtained in step S104 to obtain the substrate with the wear-resistant and hydrophobic composite coating.

[0087] In the embodiments of this application, the adhesive resin in the primary composite coating cured in step S104 is selectively etched to partially remove the surface resin. The purpose is to expose the micro-nano composite rough structure with inorganic nanoparticles as the framework, thereby achieving the target hydrophobic properties.

[0088] In some embodiments, the selective etching process includes, but is not limited to, atmospheric pressure oxygen plasma etching.

[0089] In some embodiments, the process conditions for the selective etching process include: a plasma nozzle-substrate distance of 5-20 mm, a plasma output power of 450-1000 W, and an etching time of 5-60 min.

[0090] For example, during the selective etching process, the distance between the plasma nozzle and the substrate is not limited to 10mm or 15mm, the plasma output power is not limited to 550W, 650W, 750W or 900W, and the etching time is not limited to 15min, 30min or 45min.

[0091] In some embodiments, the method for preparing the substrate with the wear-resistant hydrophobic composite coating further includes a second heat treatment step after the selective etching process.

[0092] In the embodiments of this application, the purpose of the second heat treatment is to passivate the coating surface and improve superhydrophobic stability.

[0093] In some embodiments, the process conditions for the second heat treatment include: 80-150°C in an air environment. o C holds for th, 0 < t ≤ 2h.

[0094] For example, the temperature of the second heat treatment includes, but is not limited to, 100°C, 120°C or 135°C, and the holding time includes, but is not limited to, 0.5h, 1h or 1.5h.

[0095] It should be noted that in the embodiments of this application, the order of steps S101 and S102 can be changed, or steps S101 and S102 can be performed simultaneously.

[0096] As an alternative example, a method for preparing a substrate with a wear-resistant and hydrophobic composite coating includes the following steps: S1. Substrate pretreatment: The surface of the substrate to be coated is cleaned and activated to improve the interfacial adhesion between the coating and the substrate.

[0097] S2. Preparation of composite coating solution: Inorganic nanoparticles are uniformly dispersed in an organic solvent, and then a low surface energy adhesive resin is added. After continuous stirring, a composite coating solution with uniform composition and good stability is formed.

[0098] S3. Coating application: The composite coating liquid is applied to the pretreated substrate surface by spraying, spin coating or dipping to form a wet film.

[0099] S4. Coating Curing: The wet film is heat-treated to achieve solvent evaporation and cross-linking curing of the adhesive resin. At the same time, the resin is chemically bonded to the substrate surface and the surface of inorganic nanoparticles to form a robust primary composite coating.

[0100] S5. Construction of surface hydrophobic structure: Selective etching is performed on the surface of the cured primary composite coating to partially remove the surface resin and expose the micro-nano composite rough structure with inorganic nanoparticles as the framework, thereby achieving superhydrophobic properties.

[0101] The method for preparing a substrate with a wear-resistant and hydrophobic composite coating described in this application can bring at least the following beneficial effects: 1. Hydrophobic Durability: The surface etching process is not a simple modification, but rather a subtractive manufacturing process achieved through selective etching, precisely constructing a stable micro-nano rough structure with inorganic nanoparticles as the framework. The hard nanoparticles are firmly coated and fixed by the flexible resin, forming an internally reinforced composite structure. This structure can effectively disperse and buffer external stress, greatly improving the coating's scratch resistance and wear resistance.

[0102] 2. Strong coating adhesion: The low content of inorganic nanoparticles (not exceeding 5 wt.%) solves the problem of decreased mechanical strength of the coating due to excessive content. Through dual pretreatment of the substrate and nanoparticles, the interfacial bonding between the "substrate-resin-nanoparticles" is optimized, ensuring excellent adhesion of the coating on various substrates (such as metals, polymers, ceramics, and glass).

[0103] 3. Universality: This method has a simple process and is suitable for coating large-area and complex-shaped workpieces, and has good prospects for industrialization.

[0104] <Substrate with wear-resistant and hydrophobic composite coating> The substrate with wear-resistant and hydrophobic composite coating in this application embodiment is prepared using the preparation method of the substrate with wear-resistant and hydrophobic composite coating in this application embodiment.

[0105] In some embodiments, the substrate with the wear-resistant and hydrophobic composite coating includes the substrate and the wear-resistant and hydrophobic composite coating disposed on its surface; the wear-resistant and hydrophobic composite coating includes the adhesive resin and a plurality of the inorganic nanoparticles, and the adhesive resin and the plurality of the inorganic nanoparticles together constitute a micro-nano hierarchical rough structure.

[0106] In some embodiments, a portion of the inorganic nanoparticles are distributed within the bulk phase of the adhesive resin, while another portion is embedded in the surface layer of the adhesive resin, forming multiple protrusions on the surface of the adhesive resin. In this structural configuration, the adhesive resin is analogous to the ocean within a glacier, and can be referred to as the "marine phase," while the inorganic nanoparticles are analogous to the glacier within the ocean, and can be referred to as the "glacial phase." The inorganic nanoparticles are firmly embedded in the adhesive resin, and together they constitute the aforementioned micro / nano-hierarchical rough structure.

[0107] In some embodiments, the number of inorganic nanoparticles distributed in the adhesive resin bulk phase is greater than the number of inorganic nanoparticles embedded in the adhesive resin surface layer.

[0108] In some embodiments, the inorganic nanoparticles are partially coated with the adhesive resin.

[0109] In some embodiments, the substrate having the wear-resistant hydrophobic composite coating has at least one of the following characteristics: (1) The adhesion between the wear-resistant and hydrophobic composite coating and the substrate can be above 5.0 MPa; (2) The initial water contact angle of the wear-resistant hydrophobic composite coating can be above 150°; (3) The initial roll angle of the wear-resistant and hydrophobic composite coating can be below 10°; (4) Under the conditions of using CS-10 grinding wheel and 1000g load, the Taber wear resistance test was conducted, and the water contact angle of the wear-resistant hydrophobic composite coating decreased by less than 15% after 1000 revolutions; (5) The thickness of the wear-resistant and hydrophobic composite coating is 5-120 μm.

[0110] For example, the adhesion between the wear-resistant hydrophobic composite coating and the substrate is 5.0-6.5 MPa.

[0111] For example, the initial water contact angle of the wear-resistant hydrophobic composite coating may include, but is not limited to, greater than 155°, greater than 160°, greater than 165°, or greater than 170°.

[0112] For example, the initial roll-off angle of the wear-resistant hydrophobic composite coating may include, but is not limited to, less than 9°, less than 8°, less than 7°, less than 6°, or less than 5°.

[0113] For example, the thickness of the wear-resistant hydrophobic composite coating includes, but is not limited to, 20μm, 50μm, 80μm or 100μm.

[0114] For example, the decrease rate of water contact angle after 1000 revolutions of the wear-resistant hydrophobic composite coating may be less than 12%, 10%, or less than 8%.

[0115] The substrate with wear-resistant and hydrophobic composite coating of the present application embodiment can be widely used in fields such as anti-icing, anti-fogging, self-cleaning, metal corrosion prevention, and oil-water separation.

[0116] The substrate with wear-resistant and hydrophobic composite coating and its application in the embodiments of this application have at least the beneficial effects of the preparation method of the substrate with wear-resistant and hydrophobic composite coating in the embodiments of this application.

[0117] The following non-limiting embodiments further illustrate certain features of the present technology.

[0118] I. Examples and Comparative Examples Example 1: The matrix is ​​a glass fiber epoxy composite board. The method for preparing the substrate with the wear-resistant and hydrophobic composite coating in this embodiment includes the following steps: (1) Matrix pretreatment: The glass fiber epoxy composite board was activated by atmospheric pressure air plasma for 10 seconds to obtain the pretreated matrix surface.

[0119] in: The activation treatment method and process conditions for glass fiber epoxy composite board by atmospheric pressure air plasma are as follows: a direct injection atmospheric pressure plasma treatment machine is used, the distance between the plasma nozzle and the substrate is 10mm, the plasma output power is 450W, the carrier gas is air, the input air pressure is 0.6Kpa, and the air flow rate is 60L / min.

[0120] The fiberglass epoxy composite board is an industrial FR4 epoxy board with dimensions of 500mm (length) × 500mm (width) × 1mm (thickness).

[0121] (2) Preparation of composite coating solution: Weigh 1.0 part by weight of carbon black particles with a volume equivalent particle size of 50±15nm, disperse them in 80 parts by weight of ethyl acetate, and sonicate for 2 minutes. Then add 19 parts by weight of room temperature (25℃) silicone resin, and magnetically stir at 500 rpm for 1 hour to obtain a uniform composite coating solution.

[0122] The silicone resin is a vulcanized silicone rubber of model 3145 manufactured by Dow Chemical Company.

[0123] (3) Coating application and curing: The composite coating liquid was evenly sprayed onto the pretreated substrate surface using a spray gun, and the wet film thickness was controlled to be 60±1μm. The sample was then placed in a 60℃ oven for curing for 1 hour to obtain a substrate with a primary composite coating on the surface.

[0124] (4) Construction of surface hydrophobic structure: The substrate with the primary composite coating on the surface is placed in an oxygen plasma device, and the organosilicon resin in the primary composite coating is selectively etched by oxygen plasma for 8 minutes. Then, it is heat-treated at 120°C for 1 hour to finally obtain the target composite coating with a thickness of 20±1μm, which is the substrate with wear-resistant hydrophobic composite coating in this embodiment.

[0125] in: The method and process conditions for selective etching of organosilicon resin in primary composite coating using atmospheric pressure oxygen plasma are as follows: a direct-injection atmospheric plasma treatment machine is used, the distance between the plasma nozzle and the substrate is 5 mm, the plasma output power is 1000W, the carrier gas is oxygen, the gas pressure is 0.6 kPa, and the gas flow rate is 60 L / min.

[0126] Example 2: The substrate is an aluminum alloy surface. The method for preparing the substrate with the wear-resistant and hydrophobic composite coating in this embodiment includes the following steps: (1) Substrate pretreatment: Immerse the aluminum alloy plate in 0.1 wt.% NaOH solution for 20 minutes, wash with water and ethanol, and then blow dry to hydroxylate the surface and obtain the pretreated substrate surface.

[0127] The aluminum alloy plate is grade 5052 and has dimensions of 500mm (length) × 500mm (width) × 1mm (thickness).

[0128] (2) Preparation of composite coating solution: Weigh 0.5 parts by mass of boron nitride nanosheets (volume equivalent particle size of 107±30nm), disperse them in 85 parts by mass of xylene, and sonicate for 2 minutes. After pretreatment with KH-560 silane coupling agent, add 14.5 parts by mass of room temperature (25℃) fluorinated resin, and magnetically stir at 500 rpm for 1 hour to form a uniform composite coating solution.

[0129] in: The preparation method of boron nitride nanosheets pretreated with KH-560 silane coupling agent is as follows: add 3% by weight of silane coupling agent of boron nitride to xylene dispersion of boron nitride, and stir at 40°C for 1 hour.

[0130] The fluorinated resin is FEVE (fluorinated ethylene / vinyl ether) alternating copolymer, model LF200, manufactured by AGC.

[0131] (3) Coating and curing: The composite coating liquid is applied to the pretreated substrate to form a wet film with a thickness of 300±25μm by dip coating, and then cured at 120℃ for 1 hour to obtain a substrate with a primary composite coating on the surface.

[0132] (4) Construction of surface hydrophobic structure: The substrate with the primary composite coating on the surface is placed in an oxygen plasma device, and the fluorine-containing resin in the primary composite coating is selectively etched by oxygen plasma for 10 minutes. Then, it is heat-treated at 120°C for 1 hour to finally obtain the target composite coating with a thickness of 100±15μm, which is the substrate with wear-resistant hydrophobic composite coating in this embodiment.

[0133] in: The method and process conditions for selective etching of fluorinated resin in primary composite coating using oxygen plasma are as follows: a direct-injection atmospheric plasma treatment machine is used, the distance between the plasma nozzle and the substrate is 5 mm, the plasma output power is 1000W, the gas is oxygen, the gas pressure is 0.6 kPa, and the gas flow rate is 60 L / min.

[0134] Example 3 This embodiment is basically the same as embodiment 1, except that: In step (4): The silicone resin in the primary composite coating was selectively etched using oxygen plasma for 4 minutes.

[0135] Example 4 This embodiment is basically the same as embodiment 1, except that: Step (4) involves the construction of a surface hydrophobic structure as follows: The substrate with a primary composite coating on its surface is placed in an air plasma device, and the silicone resin in the primary composite coating is selectively etched by air plasma for 8 minutes. Then, it is heat-treated at 120°C for 1 hour to finally obtain the target composite coating, which is the substrate with a wear-resistant and hydrophobic composite coating in this embodiment.

[0136] in: The method and process conditions for selective etching of silicone resin in primary composite coating using air plasma are as follows: a direct-injection atmospheric plasma treatment machine is used, the distance between the plasma nozzle and the substrate is 5 mm, the plasma output power is 1000W, the carrier gas is air, the air pressure is 0.6 kPa, and the air flow rate is 60 L / min.

[0137] Example 5 This embodiment is basically the same as embodiment 1, except that: Step (2) The composite coating solution was prepared as follows: 0.1 parts by mass of carbon black particles with an equivalent particle size of about 50 nm were weighed and dispersed in 80.9 parts by mass of ethyl acetate and sonicated for 2 minutes. Then, 19 parts by mass of room temperature (25°C) silicone resin were added and magnetically stirred at 500 rpm for 1 hour to obtain a uniform composite coating solution.

[0138] Example 6 This embodiment is basically the same as embodiment 1, except that: Step (2) The composite coating solution is prepared as follows: 2 parts by mass of carbon black particles with an equivalent particle size of about 50 nm are weighed and dispersed in 79 parts by mass of ethyl acetate, and ultrasonically homogenized for 2 minutes. Then, 19 parts by mass of room temperature (25℃) silicone resin are added, and the mixture is magnetically stirred at 500 rpm for 1 hour to obtain a uniform composite coating solution.

[0139] Example 7 This embodiment is basically the same as embodiment 1, except that: Step (2) The composite coating solution was prepared as follows: 1.0 part by weight of carbon black particles with an equivalent particle size of about 50 nm was weighed and dispersed in 89.1 parts by weight of ethyl acetate and sonicated for 2 minutes. Then, 9.9 parts by weight of room temperature (25℃) silicone resin was added and magnetically stirred at 500 rpm for 1 hour to obtain a uniform composite coating solution.

[0140] Example 8 This embodiment is basically the same as embodiment 1, except that: Step (2) The composite coating solution is prepared as follows: 1.0 part by weight of carbon black particles with an equivalent particle size of about 50 nm is weighed and dispersed in 61 parts by weight of ethyl acetate, and ultrasonically homogenized for 2 minutes. Then, 38 parts by weight of room temperature (25℃) silicone resin is added, and the mixture is magnetically stirred at 500 rpm for 1 hour to obtain a uniform composite coating solution.

[0141] Example 9 This embodiment is basically the same as embodiment 1, except that: In step (2), “organosilicon resin” is replaced with “a mixture of organosilicon resin and fluorinated resin in a mass ratio of 1:1”, wherein the organosilicon resin is the same as in Example 1, and the fluorinated resin is FEVE (fluorinated ethylene / vinyl ether) alternating copolymer of model LF200 produced by AGC.

[0142] In step (4), oxygen plasma is used to selectively etch the silicone resin and fluorinated resin in the primary composite coating for 8 minutes. Wherein: The method and process conditions for selective etching of organosilicon resin and fluorine-containing resin in primary composite coating using oxygen plasma are as follows: a direct-injection atmospheric plasma treatment machine is used, the distance between the plasma nozzle and the substrate is 5mm, the plasma output power is 1000W, the carrier gas is air, the air pressure is 0.6Kpa, and the air flow rate is 60L / min.

[0143] Example 10 This embodiment is basically the same as embodiment 1, except that: In step (2), "carbon black particles with a volume equivalent particle size of 50±15nm" is replaced with "a mixture of carbon black particles with a volume equivalent particle size of 50±15nm and silicon carbide whiskers with a diameter of 50±15nm in a mass ratio of 1:1", wherein the length of the silicon carbide whiskers is 1±0.5μm and the aspect ratio (i.e., (length / diameter)) is about 20.

[0144] Example 11 This embodiment is basically the same as embodiment 1, except that: Step (4) does not include the process of "heat treatment at 120°C for 1 hour".

[0145] Example 12 This embodiment is basically the same as embodiment 1, except that: Step (2), replace “carbon black particles with a volume equivalent particle size of 50±15nm” with “carbon black particles with a volume equivalent particle size of 260±60nm”.

[0146] Example 13 This embodiment is basically the same as embodiment 1, except that: Step (2), replace “carbon black particles with a volume equivalent particle size of about 50±15nm” with “carbon black particles with a volume equivalent particle size of 500±180nm”.

[0147] Example 14 This embodiment is basically the same as embodiment 1, except that: In step (1), the “glass fiber epoxy composite board” is replaced with “alumina (Al2O3) ceramic board”, wherein the alumina (Al2O3) ceramic board is the Keralpor 99 alumina (Al2O3) ceramic board produced by Kerafol in Germany, with a size of 200mm (length) × 200mm (width) × 1mm (thickness).

[0148] Comparative Example 1: (without nano-reinforcement phase) This comparative example is basically the same as Example 1, except that: Step (2) is as follows: 20 parts by weight of room temperature (25°C) silicone resin were dispersed in 80 parts by weight of ethyl acetate, sonicated for 2 minutes, and then magnetically stirred at 500 rpm for 1 hour to obtain the coating solution.

[0149] The silicone resin is a vulcanized silicone rubber of model 3145 manufactured by Dow Chemical Company.

[0150] In step (3), “composite coating liquid” is replaced with “coating liquid”.

[0151] Comparative Example 2: (No surface etching step) This comparative example is basically the same as Example 1, except that: Step (4) The surface hydrophobic structure is constructed by heat-treating the substrate with the primary composite coating on the surface at 120°C for 1 hour to finally obtain the target composite coating.

[0152] II. Characterization and Performance Testing 1. Morphological test The surface morphology of the target composite coatings prepared in each embodiment or comparative example was tested using scanning electron microscopy (SEM).

[0153] Figure 2 Comparative scanning electron microscope (SEM) images of the surface of the hydrophobic composite coatings prepared in Example 1 and Comparative Example 2. Figure 2 It can be seen that the target composite coating prepared in Example 1 has a micro-nano composite rough structure built with exposed carbon black particles as the skeleton, while Comparative Example 2 does not have this structure.

[0154] SEM testing of the hydrophobic composite coating prepared in Comparative Example 1 showed that the coating was flat.

[0155] 2. Coating adhesion test The adhesion of the target composite coatings prepared in each embodiment or comparative example to the substrate was tested using the pull-off method. The specific test method is GB / T 5210-2006.

[0156] The test results are shown in Table 1.

[0157] 3. Hydrophobicity test The hydrophobicity of the target composite coatings prepared in each embodiment or comparative example was tested using GB / T30693-2014 and ASTM D7334-08.

[0158] The test results are shown in Table 1.

[0159] To investigate the change in hydrophobicity before and after selective etching, the hydrophobicity of the primary composite coating on the substrate with the primary composite coating on the surface before selective etching in Example 2 was tested. The water contact angle of the primary composite coating on the substrate with the primary composite coating on the surface before selective etching was 128° and the roll-off angle was 17°. Comparing this with the hydrophobicity of the target composite coating after selective etching in Example 2 (water contact angle 150°, roll-off angle 7°) in Table 1, it can be seen that selective etching can significantly improve the hydrophobicity of the coating.

[0160] 4. Abrasion resistance test The target composite coatings prepared in each embodiment or comparative example were subjected to Taber wear resistance test under a CS-10 grinding wheel and a load of 1000g. The test method is GB / T 30314-2021.

[0161] The test results are shown in Table 1 and Figure 3 As shown.

[0162] Figure 3 This is a comparison of the water contact angle of the hydrophobic composite coatings prepared in Example 1 and Comparative Example 2 as a function of the number of friction cycles. Figure 3 It can be seen that the water contact angle of the hydrophobic composite coating (i.e. the target composite coating) prepared in Example 2 decreases slowly with the increase of wear cycles.

[0163] 5. Durability test (i.e., corrosion resistance test) The target composite coatings prepared in each embodiment or comparative example were subjected to a neutral salt spray test for 336 hours, and the test method was GB / T 10125-2021.

[0164] The test results are shown in Table 1.

[0165] Table 1 Performance Test Results

[0166] As can be seen from Table 1, the target composite coatings prepared in each embodiment of this application have better hydrophobicity, wear resistance and corrosion resistance compared with the comparative example.

[0167] Comparing Example 1 and Comparative Example 1, it can be seen that Comparative Example 1, without adding carbon black nanoparticles, only dissolved silicone rubber in ethyl acetate and then coated and cured, does not have the superhydrophobicity of the coating prepared in Example 1.

[0168] Comparing Example 1 and Comparative Example 2, it can be seen that the hydrophobic properties of the coating obtained by Comparative Example 2 without selective etching are significantly lower than those of Example 1, proving that selective etching of the surface is crucial for constructing superhydrophobic micro-nano structures.

[0169] In summary, this application has successfully prepared a composite coating that combines high wear resistance and long-lasting hydrophobicity through material structure design and process innovation, which has high practical value and market prospects.

[0170] In this application, the terms "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., refer to a specific feature, structure, material, or characteristic described in connection with that embodiment or example, which is included in at least one embodiment or example of this application. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0171] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of that feature. In the description of this application, "multiple" means at least two, such as two, three, etc., unless otherwise explicitly specified.

[0172] Although embodiments of this application have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting this application. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of this application.

Claims

1. A method for preparing a substrate with a wear-resistant and hydrophobic composite coating, characterized in that, include: The substrate surface is cleaned and / or activated to obtain a pretreated substrate surface; A composite coating solution is obtained by mixing a dispersion of inorganic nanoparticles with an adhesive resin. The composite coating liquid is formed on the surface of the pretreated substrate by coating or impregnation to obtain a substrate with a wet film on the surface; The substrate with a wet film on its surface is subjected to a first heat treatment to obtain a substrate with a primary composite coating on its surface. The adhesive resin in the primary composite coating is selectively etched to obtain the substrate with the wear-resistant and hydrophobic composite coating.

2. The preparation method according to claim 1, characterized in that, The activation treatment includes atmospheric pressure air plasma treatment; And / or, the cleaning includes at least one of alkaline soaking, alkaline washing, water washing, alcohol washing, and airflow purging.

3. The preparation method according to claim 1, characterized in that, The surface energy of the adhesive resin is less than 50 mN / m; And / or, the intrinsic water contact angle of the adhesive resin is greater than 100°; Optionally, the adhesive resin includes at least one of silicone resin and fluorinated resin.

4. The preparation method according to claim 1, characterized in that, The inorganic nanoparticles include at least one of carbon black, fumed silica, silicon carbide whiskers, carbon nanotubes, boron nitride nanosheets, and graphene. And / or, the volume equivalent particle size of the inorganic nanoparticles ranges from 20 to 500 nm; And / or, the inorganic nanoparticles are inorganic nanoparticles treated with a silane coupling agent.

5. The preparation method according to claim 1, characterized in that, The mass ratio of the inorganic nanoparticles to the adhesive resin is (0.1-2):(9.9-38). And / or, the method for preparing the substrate with the wear-resistant hydrophobic composite coating further includes: before mixing the dispersion of inorganic nanoparticles with the adhesive resin, surface-treating the inorganic nanoparticles in the dispersion of inorganic nanoparticles with a silane coupling agent. And / or, the method for preparing the substrate with the wear-resistant hydrophobic composite coating further includes: Inorganic nanoparticles are dispersed in an organic solvent to obtain a dispersion of the inorganic nanoparticles. Optionally, the mass ratio of the inorganic nanoparticles to the organic solvent is (9.9-38):(60-90).

6. The preparation method according to any one of claims 1 to 5, characterized in that, The selective etching process includes oxygen plasma etching; And / or, the process conditions for the selective etching process include: a plasma nozzle-substrate distance of 5-20 mm, a plasma output power of 450-1000 W, and an etching time of 5-60 min. And / or, the material of the substrate includes at least one of metal, polymer, ceramic, and glass; And / or, the coating method includes at least one of spraying, spin coating, and dipping; And / or, the thickness of the wet film is 10-500 μm; And / or, the first heat treatment is performed in an air atmosphere, the temperature of the first heat treatment is the curing temperature of the adhesive resin, and the time of the first heat treatment is 0.5-6 hours; And / or, the method for preparing the substrate with the wear-resistant hydrophobic composite coating further includes a second heat treatment step after the selective etching process; Optionally, the process conditions for the second heat treatment include: 80-150°C in an air environment. o C Keep t h, 0 < t ≤2h.

7. A substrate with a wear-resistant and hydrophobic composite coating, characterized in that, Prepared using the preparation method described in any one of claims 1 to 6.

8. The substrate with a wear-resistant and hydrophobic composite coating according to claim 7, characterized in that: The substrate with the wear-resistant and hydrophobic composite coating includes the substrate and the wear-resistant and hydrophobic composite coating disposed on its surface; the wear-resistant and hydrophobic composite coating includes the adhesive resin and a plurality of inorganic nanoparticles, and the adhesive resin and the plurality of inorganic nanoparticles together constitute a micro-nano hierarchical rough structure. And / or, the substrate with the wear-resistant hydrophobic composite coating has at least one of the following characteristics: (1) The adhesion between the wear-resistant and hydrophobic composite coating and the substrate can be above 5.0 MPa; (2) The initial water contact angle of the wear-resistant hydrophobic composite coating can be above 150°; (3) The initial roll angle of the wear-resistant and hydrophobic composite coating can be below 10°; (4) Under the conditions of using CS-10 grinding wheel and 1000g load, the Taber wear resistance test was conducted, and the water contact angle of the wear-resistant hydrophobic composite coating decreased by less than 15% after 1000 revolutions; (5) The thickness of the wear-resistant and hydrophobic composite coating is 5-120 μm.

9. The substrate with a wear-resistant and hydrophobic composite coating according to claim 8, characterized in that: Of the plurality of inorganic nanoparticles, a portion of the inorganic nanoparticles are distributed in the bulk phase of the adhesive resin, and another portion of the inorganic nanoparticles are embedded in the surface layer of the adhesive resin, forming a plurality of protrusions on the surface of the adhesive resin. Optionally, the number of inorganic nanoparticles distributed in the adhesive resin bulk phase is greater than the number of inorganic nanoparticles embedded in the adhesive resin surface layer.

10. The application of the substrate with wear-resistant hydrophobic composite coating as described in any one of claims 7 to 9 in the fields of anti-icing, anti-fogging, self-cleaning, metal corrosion prevention, and oil-water separation.

Images