Integrated anti-corrosion and wear-resistant coatings, composite coatings, preparation methods and applications of composite coatings

Abstract

This application provides an integrated anti-corrosion and wear-resistant coating, a composite coating, a method for preparing the composite coating, and its application. The coating for preparing the composite coating includes the following raw materials: 10-20 parts by weight of cathodic aqueous acrylic emulsion, 0.1-0.5 parts by weight of protonated modified MXene nanosheets, 60-90 parts by weight of solvent, 0.02-0.04 parts by weight of dispersant, and 0.02-0.04 parts by weight of defoamer; the protonated modified MXene nanosheets are MXene nanosheets grafted with tetrabutylphosphine hydroxide benzotriazole lignin composite material and protonated with 1 mol / L HCl. The method for preparing the composite coating includes stirring and mixing the above raw materials to obtain a mixed slurry; coating the mixed slurry onto the surface of a substrate using electrophoretic deposition technology, and curing to obtain an integrated anti-corrosion and wear-resistant composite coating. This composite coating is applied in the field of marine corrosion protection. The composite coating provided by this application has excellent anti-corrosion and wear-resistant properties.

Description

Technical Field

[0001] This application relates to the field of marine anti-corrosion and wear-resistant materials technology, and in particular to an integrated anti-corrosion and wear-resistant coating, a composite coating, a method for preparing the composite coating, and its application. Background Technology

[0002] In the marine environment, factors such as salinity, oxygen, microorganisms, and pH changes accelerate the corrosion process of metals, leading to a decrease in the strength and durability of metallic materials. Simultaneously, waves, currents, and sediments in the marine environment cause continuous mechanical wear and fatigue damage to metallic materials. These phenomena severely limit the application of metals in marine environments. my country is currently actively developing offshore wind power and deep-sea oil and gas exploration and development. However, these equipment are exposed to seawater and the marine atmosphere for extended periods, resulting in severe corrosion and wear of metallic materials. Furthermore, operating machinery often faces frictional corrosion problems. Currently used deep-sea engineering materials, such as titanium alloys, copper alloys, and nickel alloys, do not fully meet the long-life operation requirements of marine engineering equipment in rotating systems or other components. Therefore, solving the problem of component failure caused by corrosion and wear in the marine environment is a significant technical challenge facing the field of marine engineering.

[0003] To improve the corrosion and wear resistance of marine engineering equipment, innovative research is needed in material selection, surface treatment, and coating technology. Waterborne acrylic acid, due to its low volatile organic compound (VOC) content, environmental friendliness, high hardness, and good adhesion, has become a substitute for traditional organic coatings. However, waterborne acrylic acid has limitations in its anti-corrosion and lubrication properties. To enhance the corrosion and wear resistance of coatings, MXene is added as a functional filler. However, MXene's hydrophilicity makes it prone to agglomeration in water. Furthermore, the random distribution of MXene in the coating cannot meet the higher protective requirements, and its random distribution can also lead to poor coating uniformity, reduced mechanical strength, and decreased barrier properties. Summary of the Invention

[0004] This application provides an integrated anti-corrosion and wear-resistant coating, a composite coating, a method for preparing the composite coating, and its application, in order to solve the problems mentioned in the background art.

[0005] On the one hand, this application provides an integrated anti-corrosion and wear-resistant composite coating, which includes a composite coating in which protonated modified MXene nanosheets are distributed in parallel in a cathode acrylic coating.

[0006] On the other hand, this application provides a method for preparing an integrated anti-corrosion and wear-resistant composite coating, characterized in that the method for preparing the above-mentioned integrated anti-corrosion and wear-resistant composite coating includes the following steps:

[0007] 10-20 parts by weight of cathodic aqueous acrylic emulsion, 0.1-0.5 parts by weight of protonated modified MXene nanosheets, 0.02-0.04 parts by weight of dispersant, 0.02-0.04 parts by weight of defoamer, and 60-90 parts by weight of solvent are stirred and mixed to obtain a mixed slurry.

[0008] The mixed slurry is coated onto the substrate surface using electrophoretic deposition technology and then cured to obtain an integrated composite coating that is corrosion-resistant and wear-resistant.

[0009] Optionally, the conditions during the electrophoretic deposition coating process are: DC voltage controlled at 90-120V, curing temperature controlled at 120-160℃, and curing time at 30-60min.

[0010] Optionally, the preparation method of protonated MXene nanosheets includes the following steps:

[0011] Aminated MXene: MXene nanosheets, 2,5-diaminobenzenesulfonic acid and water were mixed and reacted to obtain amino-modified MXene nanosheets; the mass ratio of MXene nanosheets, 2,5-diaminobenzenesulfonic acid and water was (1-2):(1-2):1;

[0012] MXene grafted onto composite material: Amino-modified MXene nanosheets, water, and tetrabutylphosphobenzotriazole lignin composite material are mixed in a second mixture and grafted to obtain MXene nanosheets grafted onto tetrabutylphosphobenzotriazole lignin composite material.

[0013] Protonated MXene: MXene nanosheets grafted with tetrabutylphosphine hydroxide benzotriazole lignin composite material were mixed with 1 mol / L HCl solution in a third mixing process and then protonated to obtain protonated modified MXene nanosheets.

[0014] Optionally, before amination modification of MXene, MXene may be pretreated.

[0015] The preprocessing process includes:

[0016] After mixing MXene and dimethyl sulfoxide, a first centrifugation was performed. The nanosheets obtained from the first centrifugation were mixed with water and then subjected to sonication and a second centrifugation to obtain pretreated MXene nanosheets.

[0017] Optionally, the mass ratio of amino-modified MXene nanosheets, water and tetrabutylphosphine hydroxide benzotriazole lignin composite material is (1-2):(1-2):(2-3).

[0018] Optionally, the mass ratio of MXene nanosheets grafted with tetrabutylphosphohydroxybenzotriazole lignin composite material to 1 mol / L HCl solution is (1-2):(100-300).

[0019] Furthermore, this application provides an integrated anti-corrosion and wear-resistant coating, which is used to prepare the aforementioned integrated anti-corrosion and wear-resistant composite coating, or applied to the preparation method of the aforementioned integrated anti-corrosion and wear-resistant composite coating. By weight, the coating comprises the following raw materials:

[0020] The composition includes 10-20 parts by weight of cathodic aqueous acrylic emulsion, 0.1-0.5 parts by weight of protonated modified MXene nanosheets, 60-90 parts by weight of solvent, 0.02-0.04 parts by weight of dispersant, and 0.02-0.04 parts by weight of defoamer;

[0021] The protonated modified MXene nanosheets are MXene nanosheets that are grafted with tetrabutylphosphine hydroxide benzotriazole lignin composite material and protonated with 1 mol / L HCl.

[0022] Optionally, the dispersant includes one or more of BYK-104s, BYK-166, and K270;

[0023] The defoamer includes one or more of BYK-035, BYK-052N, and BYK-077; the solvent is water.

[0024] This application also provides an application of an integrated anti-corrosion and wear-resistant composite coating, which is the aforementioned integrated anti-corrosion and wear-resistant composite coating, or an integrated anti-corrosion and wear-resistant composite coating obtained by the aforementioned preparation method, and is applied in the field of marine corrosion protection.

[0025] The integrated anti-corrosion and wear-resistant coating, composite coating, preparation method of composite coating, and application provided in this application realize the preparation and application of integrated anti-corrosion and wear-resistant composite coating, and have the following beneficial effects compared with the prior art:

[0026] (1) In the composite coating provided in this application, a cathode acrylic coating is used as the substrate. The protonated modified MXene nanosheets have a positive charge on their surface, while the cathode acrylic coating has a negative charge. The protonated modified MXene nanosheets are distributed in parallel within the cathode acrylic coating, forming a continuous interface and a zigzag diffusion path. This creates a dense barrier layer between the substrate surface and the corrosive medium, significantly extending the path of the corrosive medium's penetration into the metal substrate compared to the "maze effect." Simultaneously, the parallel distribution of the protonated modified MXene nanosheets within the cathode acrylic coating makes the composite coating surface smoother and flatter, and the uniform distribution of the protonated modified MXene nanosheets in the coating improves the uniformity of the composite coating. This allows for the formation of a continuous, stable, and smooth friction protective film on the substrate surface, enabling the protonated modified MXene nanosheets to not only possess excellent lubrication performance as a wear-resistant and corrosion-resistant filler but also superior corrosion resistance.

[0027] (2) A mixed slurry was obtained by mixing the cathode aqueous acrylic emulsion, protonated modified MXene nanosheets, dispersant, defoamer, and solvent in proportion to weight. This slurry was then coated onto the substrate surface using electrophoretic deposition. Under the influence of an electric field, the protonated modified MXene nanosheets migrated towards the cathode and distributed parallel to each other within the cathode acrylic coating. This overcame the drawback of MXene nanosheets easily agglomerating in the coating, forming a composite coating with integrated anti-corrosion and wear-resistant properties. This application utilizes electrophoretic deposition technology to prepare the composite coating; the process is not only simple but also highly efficient.

[0028] (3)f + BTA-P in MXene-P nanosheets 4444 -Lig composite materials form an adsorption film on the surface of the metal substrate, preventing direct contact between the corrosive medium and the metal substrate, and BTA-P 4444 The lignin in -Lig contains phenolic hydroxyl groups, which can effectively capture oxygen free radicals, forming resonance-stabilized semiquinone free radicals, blocking chain reactions, and inhibiting metal corrosion. Simultaneously, due to f + The orientation of MXene-P has a certain angle with the crack propagation direction, which hinders the propagation of coating cracks during friction, reduces coating peeling during friction, and improves the wear resistance of the cathodic waterborne acrylic composite coating. At the same time, the polar elements N and P in the tetrabutylphosphine hydroxide benzotriazole lignin composite material will react with the metal substrate during friction to form a tribochemical film, enhancing the tribological properties of the coating.

[0029] (4) The high-performance anti-corrosion and wear-resistant integrated coating of this application uses cathodic aqueous acrylic emulsion as the base material, which is environmentally friendly, low in volatility, high in chemical stability and good adhesion. Attached Figure Description

[0030] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0031] Figure 1 f provided for an embodiment of this application + -MX-P composite coating preparation process diagram;

[0032] Figure 2 f provided for an embodiment of this application + Surface morphology and elemental composition analysis of MXene-P nanosheets Figure 2 (a) is f + TEM image of MXene-P nanosheets. Figure 2 (b) is f + SEM image of MXene-P nanosheets Figure 2 (c) is f + Ti elemental distribution map of MXene-P nanosheets measured by EDS. Figure 2 (d) is f + The N element distribution of MXene-P nanosheets as measured by EDS. Figure 2 (e) is f + - P element distribution map of MXene-P nanosheets measured by EDS;

[0033] Figure 3 MX, f-MX, f are provided in one embodiment of this application + -MX, f-MX-P, f + Potential analysis diagram of the MX-P surface;

[0034] Figure 4 These are test graphs showing the wear resistance of the composite coatings provided in Comparative Examples 1, 2, 3, and 3 of this application. Figure 4 Figure (a) shows the friction coefficient analysis of the composite coating. Figure 4 (b) shows the wear volume analysis diagram of the composite coating;

[0035] Figure 5 These are SEM images of the wear trajectories of the composite coatings provided in Comparative Examples 1, 2, 3 and 3 of this application. Figure 5 In the middle (a), the SEM image of the wear trajectory of Comparative Example 1 (WAA) is shown. Figure 5(b) shows the SEM topography of the wear trajectory in Comparative Example 2 (MX / WAA). Figure 5 (c) is the comparative example 3 (f) + SEM topography of the wear trajectory of -MX / WAA. Figure 5 (d) is Example 3 (f) + SEM topography of the wear trajectory of (-MX-P / WAA). Detailed Implementation

[0036] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions in the embodiments of this application are described clearly and completely below. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort are also within the scope of protection of this application.

[0037] On the one hand, this application provides an integrated anti-corrosion and wear-resistant composite coating, the coating comprising a composite coating in which protonated modified MXene nanosheets are distributed in parallel within a cathode acrylic coating.

[0038] Specifically, MXene nanosheets have a two-dimensional layered structure. Their excellent corrosion resistance and self-lubricating properties make them suitable fillers in coatings. The distribution orientation of MXene nanosheets in coatings can be categorized into three types: vertical, random, and parallel. MXene nanosheets distributed perpendicular to the horizontal direction of the coating have 0% barrier effect against corrosive media. Randomly distributed MXene nanosheets in the coating result in a barrier effect ranging from 0% to 100%. Random distribution can easily lead to irregular arrangement of nanosheets, agglomeration within the coating, or increased porosity, which not only negatively impacts the coating's corrosion resistance but also causes uneven shear stress distribution during friction, leading to coating peeling and reduced wear resistance. Conversely, when MXene nanosheets are distributed parallel to the horizontal direction of the coating, the barrier effect against corrosive media can reach 100%.

[0039] In the composite coating provided in this application, a cathode acrylic coating is used as the substrate. Protonated modified MXene nanosheets carry a positive charge on their surface, while the cathode acrylic coating carries a negative charge. The protonated modified MXene nanosheets are oriented and parallelly distributed within the cathode acrylic coating, forming a continuous interface and a zigzag diffusion path. This creates a dense barrier layer between the substrate surface and the corrosive medium, significantly extending the diffusion path of the corrosive medium into the metal substrate compared to the "maze effect." Simultaneously, the parallel distribution of the protonated modified MXene nanosheets within the cathode acrylic coating results in a smoother and more even surface, enhanced mechanical strength, and improved uniformity. This uniform distribution of the protonated modified MXene nanosheets further improves the uniformity of the composite coating, enabling the formation of a continuous, stable, and smooth friction protective film on the substrate surface, which is beneficial for improving the wear resistance of the composite coating. Therefore, the composite coating provided in this application exhibits excellent integrated corrosion resistance and wear resistance.

[0040] On the other hand, such as Figure 1 As shown, this application provides a method for preparing an integrated anti-corrosion and wear-resistant composite coating, which is used to prepare the above-mentioned integrated anti-corrosion and wear-resistant composite coating. The preparation method includes the following steps:

[0041] 10-20 parts by weight of cathodic aqueous acrylic emulsion, 0.1-0.5 parts by weight of protonated modified MXene nanosheets, 0.02-0.04 parts by weight of dispersant, 0.02-0.04 parts by weight of defoamer, and 60-90 parts by weight of solvent are stirred and mixed to obtain a mixed slurry.

[0042] The mixed slurry is coated onto the substrate surface using electrophoretic deposition technology and then cured to obtain an integrated composite coating that is corrosion-resistant and wear-resistant.

[0043] Specifically, a mixed slurry is obtained by stirring and mixing a cathode aqueous acrylic emulsion, protonated modified MXene nanosheets, a dispersant, a defoamer, and a solvent. This slurry is then coated onto the substrate surface using electrophoretic deposition and cured to obtain an integrated anti-corrosion and wear-resistant composite coating. The protonated modified MXene nanosheets carry a positive charge, while the cathode acrylic coating carries a negative charge. Under the influence of an electric field, the protonated modified MXene nanosheets are oriented and parallel to each other within the cathode acrylic coating, overcoming the tendency of MXene nanosheets to aggregate in the coating and forming a composite coating with integrated anti-corrosion and wear-resistant properties. Simultaneously, the protonated modified MXene nanosheets form a continuous interface and a zigzag diffusion path within the cathode acrylic coating, significantly extending the path of the corrosive medium penetrating into the metal substrate compared to the "maze effect."

[0044] The aqueous acrylic emulsion serves as the coating substrate. The dispersant's role is to prevent the center of gravity of the protonated modified MXene nanosheets from settling, maintaining the nanosheets in suspension, and thus ensuring the uniformity of the coating. The defoamer's role is to prevent the formation of bubbles in the aqueous acrylic emulsion or to eliminate any existing bubbles.

[0045] The cathode aqueous acrylic emulsion is a copolymer of acrylate and methacrylate monomers, and its solid content is 8%-12%. Electrophoretic deposition technology has the advantages of being environmentally friendly and easy to operate, and can achieve the parallel distribution of protonated modified MXene nanosheets in the aqueous cathode acrylic coating, meeting the higher protection requirements of the coating.

[0046] During the preparation of the mixed slurry, the stirring speed is 300-500 rpm, preferably 320-480 rpm, more preferably 340-460 rpm; the stirring time is preferably 50-80 min, more preferably 55-75 min, and most preferably 60-70 min.

[0047] This application achieves the preparation of an integrated anti-corrosion and wear-resistant composite coating through the above-mentioned scheme. By mixing the cathode aqueous acrylic emulsion, protonated modified MXene nanosheets, dispersant, defoamer and solvent in the indicated weight proportions, a mixed slurry is obtained. The mixed slurry is then coated onto the substrate surface using electrophoretic deposition technology. Under the influence of an electric field, the protonated modified MXene nanosheets are oriented and parallelly distributed in the cathode acrylic coating, overcoming the disadvantage that MXene nanosheets are prone to agglomeration in the coating, thus forming a composite coating with integrated anti-corrosion and wear-resistant properties.

[0048] Optionally, the conditions during the electrophoretic deposition coating process are: DC voltage controlled at 90-120V, curing temperature controlled at 120-160℃, and curing time at 30-60min.

[0049] Specifically, by controlling the voltage and temperature during the electrophoretic deposition process, the protonated modified MXene nanosheets are ensured to be distributed in parallel within the cathode acrylic coating, thereby forming a continuous, stable, and smooth composite coating, which is beneficial for improving the corrosion resistance and wear resistance of the substrate surface.

[0050] The DC voltage for electrophoretic deposition is preferably 90V-120V, more preferably 95-110V, and most preferably 100-105V. The curing temperature is preferably 120-160℃, more preferably 130-150℃, and most preferably 135-145℃. The curing time is preferably 30-60min, more preferably 35-45min, and most preferably 38-43min.

[0051] In this application, the thickness of the high-performance anti-corrosion and wear-resistant integrated coating obtained by electrophoretic deposition is preferably 40-60μm, more preferably 45-58μm, and most preferably 50-55μm.

[0052] like Figure 1 As shown, optionally, the preparation method of protonated MXene nanosheets includes the following steps:

[0053] Aminated MXene: MXene nanosheets, 2,5-diaminobenzenesulfonic acid and water were mixed and reacted to obtain amino-modified MXene nanosheets; the mass ratio of MXene nanosheets, 2,5-diaminobenzenesulfonic acid and water was (1-2):(1-2):1;

[0054] MXene grafted onto composite material: Amino-modified MXene nanosheets, water, and tetrabutylphosphobenzotriazole lignin composite material are mixed in a second mixture and grafted to obtain MXene nanosheets grafted onto tetrabutylphosphobenzotriazole lignin composite material.

[0055] Protonated MXene: MXene nanosheets grafted with tetrabutylphosphine hydroxide benzotriazole lignin composite material were mixed with 1 mol / L HCl solution in a third mixing process and then protonated to obtain protonated modified MXene nanosheets.

[0056] Specifically, MXene nanosheets have active functional groups on their surface. The amino groups on 2,5-diaminobenzenesulfonic acid form covalent bonds and intermolecular hydrogen bonds with the active groups on the surface of MXene nanosheets. The MXene nanosheets are modified by amination with 2,5-diaminobenzenesulfonic acid to enhance their hydrophilicity, thereby enhancing the dispersibility of MXene in waterborne acrylic coatings and improving the uniformity of the composite coating.

[0057] In the amination modification step of MXene, 2,5-diaminobenzenesulfonic acid is preferably chemically pure. The first mixing is carried out under stirring conditions, with the stirring speed preferably being 200-300 rpm, more preferably 220-280 rpm, and most preferably 240-260 rpm. The stirring time is preferably 0.5-3 h, more preferably 2-3 h, and most preferably 2 h; the stirring temperature is preferably 75-85℃, more preferably 80-85℃, and most preferably 80℃; the stirring temperature is preferably achieved by oil bath heating. The mass ratio of MXene nanosheets, 2,5-diaminobenzenesulfonic acid, and water is preferably (1-2):(1-2):1, more preferably 2:(1-2):1, and most preferably 2:1:1.

[0058] After amination modification, the process preferably includes sequential vacuum filtration and drying. This application does not impose any special limitations on the vacuum filtration process; conventional vacuum filtration using a filter membrane well-known to those skilled in the art is sufficient. In this application, the drying method is preferably oven drying, with a preferred drying temperature of 60°C and a preferred drying time of 12 hours.

[0059] Due to the tetrabutyl hydroxide benzotriazole lignin composite material (BTA-P) 4444 The lignin in BTA-P contains a large number of benzene rings and hydroxyl groups, giving it strong interfacial adsorption properties. 4444 -Lig was successfully loaded onto f-MX nanomaterials via intermolecular hydrogen bonds. And BTA-P 4444 The lignin in the -Lig compound contains phenolic hydroxyl groups, which can effectively capture oxygen free radicals, forming resonantly stable semiquinone free radicals, blocking chain reactions, and inhibiting metal corrosion. Simultaneously, the polar elements N and P in the tetrabutylphosphine hydroxide benzotriazole lignin composite material react with the metal substrate during friction to form a tribochemical film, preventing direct contact between the corrosive medium and the substrate surface, thus enhancing the tribological properties of the composite coating. Furthermore, due to the green, environmentally friendly, and excellent anti-corrosion and lubrication properties of the tetrabutylphosphine hydroxide benzotriazole lignin composite material, the wear resistance of the composite coating can be further improved.

[0060] More preferably, in the MXene grafted composite material, after ultrasonically mixing aminated MXene nanosheets and water, tetrabutylphosphohydroxybenzotriazole lignin composite material is added for a second mixing. The ultrasonic mixing frequency is preferably 40-80 kHz, more preferably 60-80 kHz, and most preferably 60 kHz; the ultrasonic mixing time is preferably 0.5-1.5 h, more preferably 1-1.2 h, and most preferably 1 h. This application does not impose any special limitations on the addition process of the tetrabutylphosphohydroxybenzotriazole lignin composite material, and any process well known to those skilled in the art can be used. The second mixing is carried out under stirring conditions, the stirring temperature is preferably 80-90℃, more preferably 85-90℃, and most preferably 85℃; the stirring time is preferably 18-24 h, more preferably 20-24 h, and most preferably 20 h; the stirring speed is preferably 200-300 rpm, more preferably 250-300 rpm, and most preferably 250 rpm; the stirring temperature is preferably achieved by oil bath heating.

[0061] After grafting, the process preferably includes sequential vacuum filtration, washing, and drying. This application does not impose any special limitations on the vacuum filtration process; conventional vacuum filtration using a filter membrane well-known to those skilled in the art is sufficient. In this application, washing is preferably performed with deionized water. This invention does not impose any special limitations on the number of washing cycles; a number of cycles well-known to those skilled in the art is acceptable. In this invention, drying is preferably performed by baking, with a preferred drying temperature of 60°C and a preferred drying time of 12 hours.

[0062] In this application, the preparation method of the tetrabutylphosphine hydroxide benzotriazole lignin composite material includes the following steps:

[0063] 0.4 mol of benzotriazole and 0.4 mol of tetrabutylphosphine hydroxide were added to a 500 mL single-necked flask and reacted under nitrogen protection for 24 hours. After the reaction was completed, the water was distilled off under reduced pressure, dissolved in dichloromethane, and dried overnight with anhydrous magnesium sulfate. The solvent was filtered and distilled off under reduced pressure to obtain a pale yellow transparent oily liquid, which is the ionic liquid tetrabutylphosphine hydroxide benzotriazole (named BTA-P). 4444 The yield was 95%. 5 grams of lignin were weighed and added to 95g of BTA-P. 4444 In a medium, heat to 150℃ and stir for 10 min to obtain tetrabutylphosphine hydroxide benzotriazole lignin composite material (named BTA-P). 4444 -Lig).

[0064] Simultaneously, MXene nanosheets grafted with tetrabutylphosphine hydroxide benzotriazole lignin composite material were protonated using a 1 mol / L HCl solution to obtain protonated modified MXene nanosheets. These protonated modified MXene nanosheets were then distributed parallel to each other in the cathode acrylic coating using electrophoretic deposition, overcoming the disadvantage of MXene nanosheets easily agglomerating in the coating. Furthermore, the parallel arrangement of the protonated modified MXene nanosheets formed a continuous interface and a zigzag diffusion path in the cathode acrylic coating, greatly extending the path of corrosive media penetration into the metal substrate, resulting in excellent corrosion resistance. During friction, the orientation of the protonated modified MXene nanosheets at a certain angle to the crack propagation direction hinders the propagation of coating cracks, reduces coating peeling during friction, and improves the wear resistance of the cathode waterborne acrylic composite coating. The third mixing was carried out under stirring conditions at room temperature for a preferred stirring time of 10-15 hours, more preferably 11-13 hours, and most preferably 12 hours. The stirring speed is preferably 200-300 rpm, more preferably 250-300 rpm, and most preferably 250 rpm.

[0065] After protonation, the process preferably includes sequential vacuum filtration, washing, and drying. This application does not impose any special limitations on the vacuum filtration process; conventional vacuum filtration using a filter membrane well-known to those skilled in the art is sufficient. In this application, washing is preferably performed with deionized water. This invention does not impose any special limitations on the number of washing cycles; a number of cycles well-known to those skilled in the art is acceptable. In this invention, drying is preferably performed by baking, with a preferred drying temperature of 60°C and a preferred drying time of 12 hours.

[0066] Optionally, before amination modification of MXene, MXene may be pretreated.

[0067] The preprocessing process includes:

[0068] After mixing MXene and dimethyl sulfoxide, a first centrifugation was performed. The nanosheets obtained from the first centrifugation were mixed with water and then subjected to sonication and a second centrifugation to obtain pretreated MXene nanosheets.

[0069] Specifically, by stirring and mixing MXene and dimethyl sulfoxide (DMSO), the interlayer spacing of MXene is increased by DMSO. Subsequent ultrasonic dispersion further separates the MXene into layers, yielding pretreated MXene nanosheets. These pretreated MXene nanosheets are then used for subsequent amination modification. Increasing the interlayer spacing of MXene with DMSO is beneficial for subsequent amination modification and BTA-P. 4444 The successful completion of the -Lig grafting process improves the efficiency of the amination reaction and contributes to the BTA-P... 4444 -Lig grafting.

[0070] The preferred ratio of MXene to dimethyl sulfoxide is 1 g: 50-150 mL, more preferably 1 g: 100-150 mL, and most preferably 1 g: 150 mL. The mixing of MXene and dimethyl sulfoxide is preferably carried out under stirring conditions. The stirring temperature is preferably 50-65°C, more preferably 60-65°C, and most preferably 60°C; the stirring time is preferably 18-30 h, more preferably 24-30 h, and most preferably 24 h; the stirring speed is preferably 200-300 rpm, more preferably 250-300 rpm, and most preferably 250 rpm; the stirring temperature is preferably achieved by oil bath heating.

[0071] The preferred rotation speed for the first centrifugation is 3000-3600 rpm, more preferably 3100-3500 rpm, and most preferably 3200-3300 rpm; the preferred centrifugation time is 3-5 min, more preferably 3.5-4.5 min, and most preferably 3.8-4.2 min. The nanosheets obtained from the first centrifugation are mixed with water and subjected to ultrasonication and a second centrifugation. Residual dimethyl sulfoxide is removed by washing with water to remove impurities from the MXene nanosheets. The MXene nanosheets are preferably Ti3C2 MXene; the preferred particle size of the MXene nanosheets is 300 mesh, and the preferred purity is greater than 99%.

[0072] In this application, the water is preferably deionized water or ultrapure water. The ratio of the product obtained after the first centrifugation to water is preferably 1g:500-1000mL, more preferably 1g:800-1000mL, and most preferably 1g:1000mL. In this application, the ultrasonic frequency is preferably 40-80kHz, more preferably 60-80kHz, and most preferably 60kHz. The ultrasonic time is preferably 18-30h, more preferably 24-30h, and most preferably 24h.

[0073] In this application, the rotation speed of the second centrifugation is preferably 8500-9500 rpm, more preferably 8800-9200 rpm, and most preferably 8900-9100 rpm; the time of the second centrifugation is preferably 8-15 min, more preferably 10-15 min, and most preferably 10 min.

[0074] After the second centrifugation is completed, drying is also preferably performed. The drying temperature is preferably 50-65°C, more preferably 60-65°C, and most preferably 60°C. The drying time is preferably 10-15 hours, more preferably 12-15 hours, and most preferably 12 hours.

[0075] Optionally, the mass ratio of amino-modified MXene nanosheets, water, and tetrabutylphosphohydroxybenzotriazole lignin composite material is (1-2):(1-2):(2-3). More preferably, it is 1:1:(2-3), and most preferably, it is 1:1:2.

[0076] Optionally, the mass ratio of MXene nanosheets grafted with tetrabutylphosphine hydroxide benzotriazole lignin composite material to 1 mol / L HCl solution is (1-2):(100-300). More preferably, it is 1:(100-250), and most preferably, it is 1:200.

[0077] Furthermore, this application provides an integrated anti-corrosion and wear-resistant coating, which is used to prepare the aforementioned integrated anti-corrosion and wear-resistant composite coating, or applied to the preparation method of the aforementioned integrated anti-corrosion and wear-resistant composite coating. By weight, the coating comprises the following raw materials:

[0078] The composition includes 10-20 parts by weight of cathodic aqueous acrylic emulsion, 0.1-0.5 parts by weight of protonated modified MXene nanosheets, 60-90 parts by weight of solvent, 0.02-0.04 parts by weight of dispersant, and 0.02-0.04 parts by weight of defoamer;

[0079] The protonated modified MXene nanosheets are MXene nanosheets that are grafted with tetrabutylphosphine hydroxide benzotriazole lignin composite material and protonated with 1 mol / L HCl.

[0080] Specifically, the cathode aqueous acrylic emulsion is preferably 12-18 parts by weight, more preferably 13-16 parts by weight. The protonated modified MXene nanosheets are preferably 0.2-0.4 parts by weight, more preferably 0.25-0.35 parts by weight. The dispersant is preferably 0.022-0.038 parts, more preferably 0.025-0.035 parts. The solvent is preferably 65-85 parts, more preferably 70-80 parts. In this application, the solvent is preferably water, more preferably deionized water.

[0081] Optionally, the dispersant includes one or more of BYK-104s, BYK-166, and K270;

[0082] The defoamer includes one or more of BYK-035, BYK-052N, and BYK-077; the solvent is water. When the dispersant / defoamer is two or more of the above-mentioned specific selections, this application does not have any special limitation on the ratio of the above-mentioned specific substances, and they can be mixed in any ratio.

[0083] This application also provides an application of an integrated anti-corrosion and wear-resistant composite coating. This integrated anti-corrosion and wear-resistant composite coating is the one described above, or an integrated anti-corrosion and wear-resistant composite coating obtained using the above preparation method. This integrated anti-corrosion and wear-resistant composite coating is applied in the field of marine corrosion protection. The preferred application of this composite coating is in the metal of submarine propeller shaft sleeves or transmission components of offshore oil platforms. This application does not impose any special limitations on the application method; any method well-known to those skilled in the art can be used.

[0084] The technical solution of this application will be illustrated in detail below with specific embodiments.

[0085] Preparation of protonated modified MXene nanosheets:

[0086] 1 g of Ti3C2 MXene (300 mesh particle size) and 150 mL of dimethyl sulfoxide (DMSO) were added to a round-bottom flask and mixed. The mixture was stirred at a constant temperature of 60 °C in an oil bath for 24 hours. The resulting mixture was separated by centrifugation (3200 rpm for 4 min), washed twice with water, and 0.5 g of the centrifuged nanosheets were added to 500 mL of deionized water. The mixture was ultrasonically dispersed for 24 h (60 kHz), centrifuged (9000 rpm for 10 min), and dried in an oven at 60 °C for 12 h to obtain the pretreated MXene.

[0087] 0.2 g of 2,5-diaminobenzenesulfonic acid was dissolved in 200 mL of ultrapure water to prepare a mixed solution, and then 0.4 g of MXene nanosheets were added to it. The mixture was stirred vigorously at room temperature for 0.5 hours (250 rpm) to ensure complete dispersion. Afterwards, it was stirred vigorously at 80 °C for 2 hours, then vacuum filtered through a filter membrane, and dried in an oven at 60 °C for 12 hours to obtain aminated MXene nanosheets (named f-MXene).

[0088] 0.2 g of aminated MXene nanosheets were dissolved in 200 mL of deionized water and sonicated for 1 hour (ultrasound frequency 60 kHz) to obtain a uniform dispersion. Then, 0.4 g of tetrabutylphosphine hydroxide benzotriazole lignin composite material (BTA-P) was added. 4444 -Lig), heated to 90℃, stirred continuously for 20h (speed 250rpm), vacuum filtered with a filter membrane, washed several times with deionized water, and dried in an oven at 60℃ for 12h to obtain composite material grafted MXene nanosheets (named: f-MXene-P).

[0089] 0.2 g of MXene nanosheets grafted with tetrabutylphosphohydroxybenzotriazole lignin composite material were added to 200 mL of 1 mol / L HCl solution and stirred at room temperature for 12 h at 250 rpm. After vacuum filtration through a filter membrane, the nanosheets were washed several times with deionized water and dried in an oven at 60 °C for 12 h to obtain protonated modified MXene nanosheets (named: f). + -MXene-P).

[0090] Example 1

[0091] A corrosion-resistant and wear-resistant integrated composite coating, its preparation method and application, comprising the following steps:

[0092] (1) Raw materials for composite coating preparation: by weight: 10-20 parts by weight of cathodic aqueous acrylic emulsion (specifically, the type is aqueous acrylic copolymer of acrylate and methacrylate monomers, purchased from Jiangxi Gaojie Technology Co., Ltd.), 0.1 parts by weight of protonated modified MXene nanosheets, 0.02 parts by weight of dispersant, 0.02 parts by weight of defoamer and 60 parts by weight of solvent are stirred and mixed to obtain a mixed slurry (i.e. coating).

[0093] (2) Preparation of composite coating:

[0094] The mixed slurry was coated onto the substrate surface using electrophoretic deposition technology and then cured to obtain an integrated composite coating that is corrosion-resistant and wear-resistant. The conditions for the electrophoretic deposition coating process were: DC voltage controlled at 90V, curing temperature controlled at 120℃, curing time at 30min, and the thickness of the composite coating at 50μm.

[0095] Example 2

[0096] A corrosion-resistant and wear-resistant integrated composite coating, its preparation method, and its application, comprising the following steps:

[0097] (1) Raw materials for composite coating preparation: by weight: 20 parts by weight of cathodic aqueous acrylic emulsion (specifically, the type is aqueous acrylic copolymer of acrylate and methacrylate monomers, purchased from Jiangxi Gaojie Technology Co., Ltd.), 0.5 parts by weight of protonated modified MXene nanosheets, 0.04 parts by weight of dispersant, 0.04 parts by weight of defoamer and 90 parts by weight of solvent are stirred and mixed to obtain a mixed slurry (i.e. coating).

[0098] (2) Preparation of composite coating:

[0099] The mixed slurry was coated onto the substrate surface using electrophoretic deposition technology and then cured to obtain an integrated composite coating that is corrosion-resistant and wear-resistant. The conditions for the electrophoretic deposition coating process were: DC voltage controlled at 120V, curing temperature controlled at 160℃, curing time at 60min, and the thickness of the composite coating was 52μm.

[0100] Example 3

[0101] A corrosion-resistant and wear-resistant integrated composite coating, its preparation method, and its application, comprising the following steps:

[0102] (1) Raw materials for composite coating preparation: by weight: 16 parts by weight of cathodic aqueous acrylic emulsion (specifically, the type is aqueous acrylic copolymer of acrylate and methacrylate monomers, purchased from Jiangxi Gaojie Technology Co., Ltd.), 0.35 parts by weight of protonated modified MXene nanosheets, 0.035 parts by weight of dispersant, 0.035 parts by weight of defoamer and 80 parts by weight of solvent are stirred and mixed to obtain a mixed slurry (i.e. coating).

[0103] (2) Preparation of composite coating:

[0104] The mixed slurry was coated onto the substrate surface using electrophoretic deposition technology and then cured to obtain an integrated composite coating that is corrosion-resistant and wear-resistant. The conditions for the electrophoretic deposition coating process were: DC voltage controlled at 105V, curing temperature controlled at 145℃, curing time at 43min, and the thickness of the composite coating was 54μm.

[0105] Comparative Example 1

[0106] A mixture of 15 parts of waterborne acrylic cathodic electrophoretic paint (specifically, a waterborne acrylic copolymer of acrylate and methacrylate monomers, purchased from Jiangxi Gaojie Technology Co., Ltd.), 0.025 parts of dispersant (BYK-166), 0.025 parts of defoamer (BYK-052N), and 80 parts of solvent (deionized water) was prepared and mixed at 400 rpm for 70 min. Finally, the waterborne acrylic cathodic electrophoretic paint, an integrated anti-corrosion and wear-resistant coating, was applied to the surface of Q235 steel using electrophoretic deposition technology and cured at 140℃ for 40 min to obtain a waterborne acrylic cathodic electrophoretic paint coating (WAA) with a thickness of 53 μm.

[0107] Comparative Example 2

[0108] A mixture of 15 parts waterborne acrylic cathodic electrophoretic paint, 0.3 parts MXene nanosheets, 0.025 parts dispersant (BYK-166), 0.025 parts defoamer (BYK-052N), and 80 parts solvent (deionized water) was prepared and mixed at 400 rpm for 70 min. Finally, the waterborne acrylic cathodic electrophoretic paint anti-corrosion and wear-resistant integrated coating was applied to the surface of Q235 steel using electrophoretic deposition technology. After curing at 140℃ for 40 min, a high-performance waterborne acrylic cathodic electrophoretic paint anti-corrosion and wear-resistant integrated coating (MXene / WAA) was obtained with a composite coating thickness of 56 μm.

[0109] Comparative Example 3

[0110] 15 parts of water-based acrylic cathodic electrophoresis paint, aminated and protonated MXene nanosheets (f + A mixture of 0.3 parts of MXene nanosheets, 0.025 parts of dispersant (BYK-166), 0.025 parts of defoamer (BYK-052N), and 80 parts of solvent (deionized water) was prepared and mixed at 400 rpm for 70 min. Finally, the water-based acrylic cathodic electrophoretic coating, integrating anti-corrosion and wear resistance, was coated onto the surface of Q235 steel using electrophoretic deposition technology. After curing at 140℃ for 40 min, a high-performance water-based acrylic cathodic electrophoretic coating integrating anti-corrosion and wear resistance was obtained. +-MXene / WAA), the thickness of the composite coating is 54μm.

[0111] Among them, f + -MX (i.e., f) + The preparation method of (-MXene) is as follows: 0.2 g of aminated MXene was added to 200 mL of 1 mol / L HCl solution, and stirred at room temperature at 250 rpm for 12 h. After vacuum filtration through a filter membrane, it was washed several times with deionized water and dried in an oven at 60 °C for 12 h to obtain f + -MXene.

[0112] Experimental Example 1

[0113] f was examined using transmission electron microscopy (TEM, TF20), scanning electron microscopy (SEM, fg-250), and energy-dispersive spectroscopy (EDS). + The surface morphology and elemental composition of MXene-P nanosheets were analyzed. The results are as follows: Figure 2 As shown. Figure 2 (a) is f + TEM image of MXene-P nanosheets Figure 2 (b) is f + SEM image of MXene-P nanosheets Figure 2 (c) is f + Ti elemental distribution map of MXene-P nanosheets measured by EDS. Figure 2 (d) is f + The N element distribution of MXene-P nanosheets as measured by EDS. Figure 2 (e) is f + P element distribution map of MXene-P nanosheets measured by EDS.

[0114] observe Figure 2 (a) and Figure 2 From (b), we can see that f + MXene-P nanosheets are two-dimensional sheet-like structures with a certain degree of transparency. And through... Figure 2 (c) Figure 2 (d) and Figure 2 In (e), it was observed that in f + A large amount of N and P elements were detected in the EDS energy spectrum of MXene-P nanosheets, which corresponds to BTA-P 4444 The presence of N and P elements in the tetrabutylphosphine hydroxide benzotriazole ionic liquid in the -Lig composite material also indicates that 2,5-diaminobenzenesulfonic acid has been used to modify MXene nanosheets.

[0115] Experiment Example 2

[0116] Zate potentiometer (DLS) was used to analyze MX (MXene nanosheets), f-MX, and f + -MX, f-MX-P, f + The potential changes on the MX-P surface were analyzed, and the results are as follows: Figure 3 As shown, Figure 3 For MX, f-MX, f + -MX, f-MX-P, f + Potential analysis diagram of the MX-P surface.

[0117] Depend on Figure 3 The Zeta potentials of MX, f-MX, and f-MX-P are -12.3mV, -22.4mV, and -14.3mV, respectively, indicating that the surfaces of MX, f-MX, and f-MX-P are negatively charged. Meanwhile, f... + -MX、f + The Zate potentials of -MX-P are 5.7 mV and 12.1 mV, respectively, and the surface carries a positive charge. This is due to the -NH3 group after protonation. + Its cationic properties make f + -MX、f + The -MX-P surface acquires a positive charge. This further demonstrates that protonation of f-MX and f-MX-P with a 1 mol / L hydrochloric acid solution can imbue their surfaces with a positive charge, paving the way for the preparation of parallel-aligned f-MX-P surfaces using electrophoretic deposition. + -MX / WAA, f + -MX-P / WAA composite coating creates the conditions.

[0118] Experimental Example 3

[0119] Electrochemical impedance spectroscopy (EIS) method for testing the corrosion resistance of composite coatings

[0120] Electrochemical workstation was used to study WAA (Comparative Example 1), MX / WAA (Comparative Example 2), and f + -MX / WAA (Comparative Example 3), f + The corrosion resistance of MX-P / WAA (Example 3) was tested by immersion in 3.5 wt.% NaCl solution for 1 day, 7 days, 14 days, and 27 days. A conventional three-electrode system was used, with a surface exposure area of ​​1 cm². 2 The aqueous acrylic composite coating / Q235 steel sample was used as the working electrode, the calomel electrode (SCE) as the reference electrode, and the platinum electrode as the counter electrode. Electrochemical impedance spectroscopy (EIS) was performed at a frequency range of 10 Hz. -2 -10 5The Hz frequency and AC amplitude were 10mV. The test was conducted after the open circuit potential stabilized. The EIS data of the composite coating under different immersion times (1d, 7d, 14d, 27d) were fitted and analyzed using ZsimpWin software. The data are shown in Tables 1 and 2.

[0121] Table 1. Electrochemical parameters of the composite coating after immersion in 3.5 wt.% NaCl solution for 1 day.

[0122]

[0123] Table 2. Electrochemical parameters of the composite coating after immersion in 3.5 wt.% NaCl solution for 27 days.

[0124]

[0125] Q c and Q dl These represent coated capacitors and double-layer capacitors, respectively. Q c The value is used to evaluate the protective performance of the coating. Q c The higher the value, the more micropores and defects there are in the coating, and the worse the coating's corrosion resistance. dl It can reflect the corrosion activity of Q235 steel, Q dl The larger the diameter, the more severe the corrosion of Q235 steel. s R c and R ct These represent solution resistance, coating resistance, and charge transfer resistance, respectively. R c R indicates the coating's corrosion resistance. c The larger the coating, the more difficult it is for corrosive media to penetrate the coating and reach the metal substrate. Table 2 shows that f... + -MX-P / WAA (Example 3) R after immersion in a corrosive solution for 27 days c The value is 1.18 × 10 6 Ω·cm 2 The value is significantly greater than the other coating types, as shown by the data in Tables 1 and 2. + -MX-P / WAA exhibits excellent corrosion resistance. When corrosive media penetrate the composite coating, the corrosion process of the coating / metal system is controlled by the charge transfer resistance R... ct Decision, R ct The larger the diameter, the better the corrosion resistance of the coating.

[0126] Comparative analysis of Tables 1 and 2 revealed that as the WAA coating (Comparative Example 1) was immersed in 3.5 wt.% NaCl solution for 27 days, the R of WAA... ct The value ranges from 5.64 × 10 6 Ω·cm 2 Decreased to 6.09×10 4 Ω·cm2 Q c Q dl The values ​​ranged from 2.40 × 10 -10 Ω·cm -2 ·S n Decreased to 1.47 × 10 -9 Ω·cm -2 ·S n 2.80×10 -7 Ω·cm -2 ·S n Decreased to 5.68×10 -5 Ω·cm -2 ·S n This indicates that corrosive substances can penetrate the WAA coating and reach the Q235 steel substrate, causing severe corrosion to the Q235 steel. Meanwhile, the R... (The sentence is incomplete and requires further context to translate accurately.) ct The value ranges from 1.41 × 10 7 Ω·cm 2 Reduced to 6.74×10 5 Ω·cm 2 The corrosion resistance of MX / WAA is improved compared to WAA. This is because the WAA coating generates a large number of micropores and defects due to the evaporation of moisture during the curing process, providing diffusion channels for the invasion of corrosive media. MX, with its smaller layers and larger specific surface area, is added to waterborne acrylic coatings as a filler, enhancing the coating's density and creating a "maze effect" within the waterborne acrylic coating, thus extending the diffusion path of corrosive media.

[0127] When f + When -MX / WAA (Comparative Example 3) was soaked in 3.5 wt.% NaCl solution for 27 days, R ct The value is from 3.06 × 10 8 Ω·cm 2 Reduced to 1.31×10 7 Ω·cm 2 Q c Q dl The values ​​are 2.28 × 10 -10 Ω·cm -2 ·S n 6.66×10 -7 Ω·cm -2 ·S n Both are greater than MX / WAA. This indicates that f + The micropores and defects in MX / WAA are fewer than in MX / WAA, making it difficult for corrosive media to penetrate the coating micropores and reach the metal substrate. Therefore, f +-MX / WAA exhibits superior corrosion resistance compared to MX / WAA. These results indicate that the amination modification of MX using 2,5-diaminobenzenesulfonic acid and f... + -MX nanosheets are distributed parallel to each other in the coating using electrophoretic deposition, overcoming the drawbacks of random distribution and easy aggregation of MX nanosheets in the coating. Simultaneously, the parallel distribution of f... + -MX forms a continuous interface and a "zigzag effect" in water-based acrylic coatings. The parallel arrangement of MX within the coating provides superior barrier properties because this is because the parallel arrangement of MX maximizes its high specific surface area, effectively preventing corrosive substances from penetrating the metal substrate. Therefore, f + -MX / WAA exhibits superior corrosion resistance compared to MX / WAA.

[0128] f + When -MX-P / WAA (Example 3) was soaked in 3.5 wt.% NaCl solution for 27 days, R ct The value ranges from 1.97 × 10 9 Ω·cm 2 Reduced to 4.01×10 7 Ω·cm 2 f + Q in -MX-P / WAA c Q dl The values ​​are 1.79 × 10 -10 Ω·cm -2 ·S n 2.83×10 -10 Ω·cm -2 ·S n All are greater than f + -MX / WAA, this indicates f + Micropores and defects in MX-P / WAA and f + -MX / WAA further reduces the amount of corrosive media, making it difficult for f to pass through. + The micropores in the MX-P / WAA penetrate to the coating / metal interface. Therefore, f + -MX-P / WAA has significantly better corrosion resistance than f + -MX / WAA. By comparing the above experimental results, it can be seen that, on the one hand, electrophoretic deposition technology can be used to... + -MX-P was added as a coating filler to the cathode waterborne acrylic resin, f + -MX-P particles are oriented to form a continuous interface and a zigzag diffusion path in the coating, overcoming the tendency of MX particles to agglomerate in the coating. This enhances the density of the coating while extending the diffusion path of the corrosive medium. On the other hand, the load on f... + BTA-P on MX nanosheets4444 -Lig forms an adsorption film on the surface of a Q235 steel substrate, blocking the intrusion of corrosive media, and BTA-P 4444 The lignin in the -Lig composite material contains phenolic hydroxyl groups, which effectively capture oxygen free radicals and form resonantly stable semiquinone free radicals, blocking the chain reaction and thus further delaying the corrosion of Q235 steel.

[0129] Experiment Example 4

[0130] Abrasion resistance test of composite coating

[0131] Using a CSM friction and wear testing machine (Antonpa, CSM, TRB3, Switzerland), under experimental conditions of a load of 2 N, a frequency of 2 Hz, a friction range of 5 mm, and a friction time of 10 min, comparative examples 1 (WAA), 2 (MX / WAA), and 3 (f) were tested. + -MX / WAA), Example 3 (f + The coefficient of friction of the composite coating provided by -MX-P / WAA (e.g., Figure 4 The test was conducted in (a)). The wear volume of the composite coating was measured using a confocal microscope (DCM8). Figure 4 In section (b), the wear morphology of the composite coating was finally observed using field emission scanning electron microscopy, and the results are as follows: Figure 5 As shown. Figure 5 (a) shows the SEM topography of the wear trajectory of the WAA. Figure 5 (b) shows the SEM topography of the wear trajectory of MX / WAA. Figure 5 (c) is f + SEM topography of the wear trajectory of -MX / WAA Figure 5 (d) is f + SEM topography of the wear track of -MX-P / WAA.

[0132] observe Figure 4 As shown in (a), the friction coefficient of WAA begins to increase slowly in the initial stage of friction, and then increases sharply to 0.843 when the friction time increases to 100s. The friction coefficient of MX / WAA after stabilization (0.704) is lower than that of WAA. This is due to the self-lubricating properties of MX, which form a lubricating layer during friction. + The coefficient of friction of MX / WAA increases slowly in the initial stage of friction and is significantly lower than that of MX / WAA. This is because the hydrophilicity of MX modified with 2,5-diaminobenzenesulfonic acid is enhanced, which improves the dispersibility of MX in waterborne acrylic coatings. Meanwhile, f + The parallel distribution of -MX in the water-based acrylic coating makes the composite coating surface smoother and flatter. +The coefficient of friction of -MX / WAA is relatively low in the initial stage of friction, but it rises sharply to 0.655 when the friction time exceeds 500s. This is due to the increased surface roughness of the coating caused by coating wear, resulting in increased friction. + The coefficient of friction of MX-P / WAA tends to level off throughout the friction process and decreases to 0.103. This is due to the lubricating properties of MX and BTA-P. 4444 -Lig synergistic effect makes f + -MX-P / WAA's abrasion resistance ratio f + -MX / WAA is superior. Furthermore, wear volume (e.g.) Figure 4 The variation trend of (b) is similar to that of the friction coefficient, and the wear volume of the WAA coating is 6.44 × 10⁻⁶. 6 μm -3 Compared to pure WAA coatings, MX / WAA, f + -MX / WAA, f + The wear volume of the MX-P / WAA composite coating was reduced to 2.54 × 10⁻⁶. 5 μm -3 1.25×10 5 μm -3 and 7.77×10 4 μm -3 In conclusion, f + -MX-P / WAA has excellent wear resistance.

[0133] like Figure 5 As shown in (a), the wear marks on the WAA are wide and numerous wear cracks are observed. Additionally, a small amount of debris is distributed around the wear marks on the WAA. This phenomenon is caused by the water-based acrylic coating peeling off during friction, leading to wear on the Q235 steel.

[0134] The wear pattern of MX / WAA is as follows Figure 5 As shown in (b), the wear marks are narrower compared to WAA, demonstrating that MX, as a coating filler, can improve the wear resistance of the coating. + Only a few wear cracks were observed on the MX / WAA coated surface, and the wear marks were shallow (e.g. Figure 5 (c) This is due to the parallel distribution of f in the coating. + -The orientation of MX at a certain angle to the crack propagation direction hinders crack propagation and reduces coating peeling. + -MX-P / WAA wear marks such as Figure 5 As shown in (d), f + The MX-P / WAA exhibited the shallowest wear depth, and no obvious wear cracks were observed. This is due to the use of electrophoretic deposition technology to achieve the desired effect.+ -MXene-P is distributed in parallel within the coating, further reducing MX agglomeration and the concentration of shear stress during friction, thus reducing coating peeling. + The parallel distribution of MXene-P in the coating enables the rapid formation of a friction protective film covering the largest possible sliding surface area during friction, fully leveraging f + -MXene-P's self-lubricating properties. And the BTA-P loaded onto the MX... 4444 The polar elements N and P in Lig react with the metal substrate during friction to form a tribochemical reaction film, thereby further enhancing f + -MX-P / WAA composite coating's wear resistance. Therefore f + The MX-P / WAA composite coating exhibits excellent wear resistance.

[0135] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application.

Claims

1. A method for preparing an integrated anti-corrosion and wear-resistant composite coating, characterized in that, The preparation method includes the following steps: 10-20 parts by weight of cathodic aqueous acrylic emulsion, 0.1-0.5 parts by weight of protonated modified MXene nanosheets, 0.02-0.04 parts by weight of dispersant, 0.02-0.04 parts by weight of defoamer, and 60-90 parts by weight of solvent are stirred and mixed to obtain a mixed slurry. The mixed slurry is moved toward the cathode and coated onto the substrate surface by electrophoretic deposition under the action of an electric field, and then cured to obtain the anti-corrosion and wear-resistant integrated composite coating. The method for preparing the protonated MXene nanosheets includes the following steps: Aminated MXene: MXene nanosheets, 2,5-diaminobenzenesulfonic acid and water were first mixed and reacted to obtain amino-modified MXene nanosheets; the mass ratio of MXene nanosheets, 2,5-diaminobenzenesulfonic acid and water was (1-2):(1-2):1; MXene grafting in composite material: The amino-modified MXene nanosheets, water, and tetrabutylphosphobenzotriazole lignin composite material are mixed for the second time and grafted to obtain MXene nanosheets grafted with tetrabutylphosphobenzotriazole lignin composite material; the mass ratio of the amino-modified MXene nanosheets, the water, and the tetrabutylphosphobenzotriazole lignin composite material is (1-2):(1-2):(2-3). Protonated MXene: The MXene nanosheets of the grafted tetrabutylphosphine hydroxide benzotriazole lignin composite material are mixed with a 1 mol / L HCl solution in a third mixing process and then protonated to obtain the protonated modified MXene nanosheets; the mass ratio of the MXene nanosheets of the grafted tetrabutylphosphine hydroxide benzotriazole lignin composite material to the 1 mol / L HCl solution is (1-2):(100-300).

2. The method for preparing the integrated anti-corrosion and wear-resistant composite coating according to claim 1, characterized in that, The conditions for the electrophoretic deposition coating process are as follows: DC voltage controlled at 90-120V, curing temperature controlled at 120-160℃, and curing time at 30-60min.

3. The method for preparing the integrated anti-corrosion and wear-resistant composite coating according to claim 1 or 2, characterized in that, Before the amination modification of MXene, the process also includes pretreatment of MXene. The preprocessing process includes: After mixing MXene and dimethyl sulfoxide, a first centrifugation was performed. The nanosheets obtained from the first centrifugation were mixed with water and then subjected to sonication and a second centrifugation to obtain pretreated MXene nanosheets.

4. A corrosion-resistant and wear-resistant integrated composite coating, characterized in that, The coating is prepared by the method described in any one of claims 1-3 for preparing an integrated anti-corrosion and wear-resistant composite coating.

5. The anti-corrosion and wear-resistant integrated composite coating according to claim 4, characterized in that, The dispersant includes one or more of BYK-104s, BYK-166, and K270; The defoamer includes one or more of BYK-035, BYK-052N, and BYK-077; the solvent is water.

6. The application of an integrated anti-corrosion and wear-resistant composite coating, characterized in that, The integrated anti-corrosion and wear-resistant composite coating is an integrated anti-corrosion and wear-resistant composite coating obtained by the preparation method described in any one of claims 1-3, and the integrated anti-corrosion and wear-resistant composite coating is applied in the field of marine anti-corrosion.

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