Anticorrosion and wear-resistant integrated coating, preparation method and application thereof

Abstract

The present application relates to the technical field of deep-sea corrosion and wear resistance, and particularly relates to a corrosion and wear resistant integrated coating, a preparation method and application thereof.The present application provides a corrosion and wear resistant integrated coating, which comprises the following preparation raw materials in mass fraction: 20-40 parts of water-based epoxy resin, 0.1-0.5 parts of modified MXene nanosheet, 20-40 parts of curing agent, 0.01-0.05 parts of dispersing agent, 0.01-0.05 parts of defoaming agent, 0.01-0.05 parts of leveling agent and 20-40 parts of solvent; the modified MXene nanosheet is MXene nanosheet of grafted tetrabutylphosphonium hydroxide benzotriazole lignin composite material.The corrosion and wear resistant integrated coating has a low friction coefficient and excellent corrosion resistance and wear resistance in a marine environment.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of deep-sea corrosion and wear resistance, and particularly relates to a corrosion and wear resistant integrated coating, a preparation method and application thereof. BACKGROUND

[0002] In the marine environment, metal materials are damaged and fail due to the interaction of seawater corrosion and wear, which seriously restricts the application of marine materials. China is actively promoting the development and utilization of marine energy through the construction of offshore wind farms and the use of tidal energy for power generation. China has independently developed high-tech equipment that has been deployed in near-shore areas and is entering a large-scale service stage. However, these marine engineering equipment is immersed in seawater for a long time, causing the metal materials exposed to the marine atmospheric environment to be severely corroded. At the same time, various tribological problems often occur during the operation of marine engineering equipment, leading to equipment wear and damage, thereby accelerating the damage and failure of metal materials. The current deep-sea engineering equipment materials (such as titanium alloys, copper alloys and nickel alloys) cannot fully meet the long-life operation requirements of rotating systems or other components of marine engineering equipment exposed to marine environments for a long time. Therefore, how to solve the problem of component failure caused by corrosion and wear faced by rotating systems, anchor chains or other components in the marine environment is a technical problem that needs to be solved in the field of marine engineering equipment. Therefore, innovation and research are needed in the aspects of material selection, surface treatment and coating technology to improve the corrosion resistance and wear resistance of equipment components.

[0003] The volatile organic compound content in the waterborne epoxy resin is low, which does not cause air pollution, and the excellent mechanical properties, chemical stability and good adhesion to metal substrate of the waterborne epoxy resin make it be used to replace the traditional organic coating and be applied to the field of metal protection. In view of some limitations of the waterborne epoxy resin in the coating, such as insufficient lubricity and corrosion resistance, in order to meet the use requirements of equipment, a high molecular weight waterborne epoxy resin is selected as the coating base material, the high molecular weight resin has better flexibility, and can improve the solvent resistance, adhesion and substrate wettability of the coating. By using the reaction of the epoxy group in the high molecular weight waterborne epoxy resin and the polyamine curing agent for crosslinking, an excellent crosslinked network structure is formed, which can provide higher mechanical strength and wear resistance. At the same time, the long-term corrosion resistance of the coating in a humid and corrosive environment needs to be considered, and a composite functional filler, such as Ti3C2 MXene, can be added as a wear-resistant and corrosion-resistant filler to provide excellent wear resistance and corrosion resistance of the coating. However, the hydrophilicity of MXene makes it easy to agglomerate in the waterborne epoxy resin. Therefore, before the MXene powder is filled into the waterborne epoxy resin, it is necessary to modify the surface of the MXene powder to improve the interfacial compatibility between the MXene powder and the polymer and prevent agglomeration and affect the dispersibility. In summary, by selecting a high molecular weight waterborne epoxy resin, performing a crosslinking reaction and adding a composite functional filler, the wear resistance and corrosion resistance of the waterborne epoxy resin coating can be improved to meet the use requirements of marine engineering equipment in complex environments. SUMMARY

[0004] The application aims to provide a corrosion and wear resistant integrated coating and a preparation method and application thereof.

[0005] In order to achieve the above application purposes, the application provides the following technical solutions.

[0006] The application provides a corrosion and wear resistant integrated coating, which comprises the following preparation raw materials in mass parts: 20-40 parts of waterborne epoxy resin, 0.1-0.5 parts of modified MXene nanosheet, 20-40 parts of curing agent, 0.01-0.05 parts of dispersing agent, 0.01-0.05 parts of defoaming agent, 0.01-0.05 parts of leveling agent and 20-40 parts of solvent.

[0007] The modified MXene nanosheet is a MXene nanosheet of grafted tetrabutylphosphonium hydroxide benzotriazole lignin composite material.

[0008] Preferably, the preparation method of the modified MXene nanosheet comprises the following steps:

[0009] The MXene nanosheet, 2, 5-diamino benzene sulfonic acid and water are first mixed, modified to obtain the amino-modified MXene nanosheet;

[0010] The amino-modified MXene nanosheet, water and tetrabutylphosphonium hydroxide benzotriazole lignin composite material are second mixed, grafted to obtain the modified MXene nanosheet.

[0011] Preferably, before the first mixing, the MXene nanosheet is pretreated.

[0012] The pretreatment includes the following steps:

[0013] After the MXene and dimethyl sulfoxide are mixed, the first centrifugation is carried out, the nanosheet and water centrifuged out are mixed, and the ultrasonic and the second centrifugation are carried out in sequence to obtain the pretreated MXene nanosheet.

[0014] Preferably, the mass ratio of the MXene nanosheet, 2, 5-diamino benzene sulfonic acid and water is (1-2) :(1-2) :1.

[0015] The modification is carried out under stirring, the temperature of the stirring is 75-85℃, the rotation speed is 200-300rpm, and the time is 2-3h.

[0016] Preferably, the mass ratio of the amino-modified MXene nanosheet, water and tetrabutylphosphonium hydroxide benzotriazole lignin composite material is (1-2) :(1-2) :(2-3).

[0017] The grafting is carried out under stirring, the temperature of the stirring is 80-90℃, the rotation speed is 200-300rpm, and the time is 18-24h.

[0018] Preferably, the water-based epoxy resin is a bisphenol A type water-based epoxy resin, and the epoxy value of the water-based epoxy resin is 0.55-0.6.

[0019] Preferably, the curing agent is a triethylene tetramine curing agent.

[0020] The dispersant includes one or more of BYK-104s, BYK-166 and BYK-410.

[0021] Preferably, the defoaming agent includes one or more of silicone defoaming agent, BYK-052N and BYK-410.

[0022] The leveling agent includes one or more of BYK-345, BYK-300 and BYK-370.

[0023] The solvent is water.

[0024] The application further provides a preparation method of the corrosion and wear resistant integrated coating.

[0025] The water-based epoxy resin, the modified MXene nanosheet, the curing agent, the dispersing agent, the defoaming agent, the leveling agent and the solvent are mixed to obtain a mixed slurry.

[0026] The mixed slurry is sprayed on the surface of a substrate and cured to obtain the corrosion and wear resistant integrated coating.

[0027] The application further provides application of the corrosion and wear resistant integrated coating or the corrosion and wear resistant integrated coating prepared by the preparation method in the field of marine corrosion prevention.

[0028] The application provides a corrosion and wear resistant integrated coating, which comprises the following preparation raw materials in mass fractions: 20-40 parts of a water-based epoxy resin, 0.1-0.5 parts of a modified MXene nanosheet, 20-40 parts of a curing agent, 0.01-0.05 parts of a dispersing agent, 0.01-0.05 parts of a defoaming agent, 0.01-0.05 parts of a leveling agent and 20-40 parts of a solvent; the modified MXene nanosheet is a MXene nanosheet of a grafting tetrabutylphosphonium hydroxide benzotriazole lignin composite material. The MXene nanosheet of the grafting tetrabutylphosphonium hydroxide benzotriazole lignin composite material can further improve the dispersibility and interfacial compatibility of MXene in the water-based epoxy resin, thereby reducing the shear stress in the friction process and reducing the wear of the coating. Meanwhile, the polar elements N and P in the tetrabutylphosphonium hydroxide benzotriazole lignin composite material can react with the metal substrate to form a chemical film in the friction process, thereby enhancing the tribological properties of the coating. The laminated structure of the MXene can extend the penetration path of the corrosive medium due to the “labyrinth effect”, and the lignin in the tetrabutylphosphonium hydroxide benzotriazole lignin composite material contains phenolic hydroxyl groups, which can effectively capture oxygen free radicals to form a resonance-stable semiquinone radical to interrupt the chain reaction, thereby improving the corrosion resistance of the coating in the marine environment. Meanwhile, the corrosion and wear resistant integrated coating uses the water-based epoxy resin as a base material, has environmental protection, low volatility, high chemical stability and good adhesion, and the modified MXene nanosheet used as the wear-resistant and corrosion-resistant filler has excellent lubricating properties and excellent corrosion resistance, so that the corrosion resistance and friction-reducing and wear-resistant properties of the coating can be significantly improved. The corrosion and wear resistant integrated coating has good tribological properties under dry friction conditions, the coating improves the corrosion and wear resistance of the organic adhesive coating when exposed to the deep sea environment for a long time, and reduces the damage and failure problems caused by high load impact and mechanical wear. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 Physical picture of the anti-corrosion and wear-resistant integrated coating described in Example 3;

[0030] Figure 2 Anti-corrosion performance test of the anti-corrosion and wear-resistant integrated coating described in Comparative Example 1, Comparative Example 2, Comparative Example 3, and Example 3;

[0031] Figure 3 Wear resistance test of the anti-corrosion and wear-resistant integrated coating described in Comparative Example 1, Comparative Example 2, Comparative Example 3, and Example 3;

[0032] Figure 4 Wear morphology (SEM picture) of the anti-corrosion and wear-resistant integrated coating described in Comparative Example 1, Comparative Example 2, Comparative Example 3, and Example 3. DETAILED DESCRIPTION

[0033] The application provides an anti-corrosion and wear-resistant integrated coating, which comprises the following preparation raw materials in mass fraction: 20-40 parts of water-based epoxy resin, 0.1-0.5 parts of modified MXene nanosheet, 20-40 parts of curing agent, 0.01-0.05 parts of dispersing agent, 0.01-0.05 parts of defoaming agent, 0.01-0.05 parts of leveling agent and 20-40 parts of solvent.

[0034] The modified MXene nanosheet is a MXene nanosheet grafted with tetrabutylphosphonium hydroxide benzotriazole lignin composite material.

[0035] In the application, all the preparation raw materials are commercially available products well known to those skilled in the art, unless otherwise specified.

[0036] The preparation raw materials of the anti-corrosion and wear-resistant integrated coating according to the application comprise 20-40 parts of water-based epoxy resin in mass fraction, preferably 25-35 parts, and more preferably 28-32 parts. In the application, the epoxy value of the water-based epoxy resin is preferably 0.6. The water-based epoxy resin is preferably a bisphenol A type water-based epoxy resin; the bisphenol A type water-based epoxy resin is preferably one or more of BH-653, BDR6100, BD-20 and R-828, and when the bisphenol A type water-based epoxy resin is two or more of the above specific choices, the application does not have any special limitation on the ratio of the above specific substances, and they can be mixed in any ratio.

[0037] The preparation raw materials of the anti-corrosion and wear-resistant integrated coating according to the application comprise 0.1-0.5 parts of modified MXene nanosheet in mass fraction of the water-based epoxy resin, preferably 0.2-0.4 parts, and more preferably 0.25-0.35 parts.

[0038] In the present application, the preparation method of the modified MXene nanosheet preferably comprises the following steps:

[0039] The MXene nanosheet, 2, 5-diamino benzene sulfonic acid and water are first mixed for modification to obtain an aminated modified MXene nanosheet.

[0040] The aminated modified MXene nanosheet, water and tetrabutylphosphonium hydroxide benzotriazole lignin composite material are second mixed for grafting to obtain the modified MXene nanosheet.

[0041] In the present application, the MXene nanosheet, 2, 5-diamino benzene sulfonic acid and water are first mixed for modification to obtain an aminated modified MXene nanosheet.

[0042] In the present application, the MXene nanosheet is preferably Ti3C2 MXene; the particle size of the MXene nanosheet is preferably 300 mesh, and the purity is preferably greater than 99%. In the present application, the 2, 5-diamino benzene sulfonic acid is preferably chemically pure. In the present application, the water is preferably deionized water.

[0043] Before the first mixing, the present application also preferably comprises pretreating the MXene nanosheet; the pretreatment preferably comprises the following steps:

[0044] After mixing the MXene and dimethyl sulfoxide, first centrifugation is performed, the nanosheet and water centrifuged out are mixed, and ultrasonic and second centrifugation are performed in sequence to obtain the pretreated MXene nanosheet.

[0045] In the present application, the amount ratio of the MXene and dimethyl sulfoxide is preferably 1g: 50-150mL, more preferably 1g: 100-150mL, and most preferably 1g: 150mL.

[0046] In the present application, the mixing of the MXene and dimethyl sulfoxide is preferably performed under stirring, the stirring temperature is preferably 50-65℃, more preferably 60-65℃, and most preferably 60℃; the stirring time is preferably 18-30h, more preferably 24-30h, and most preferably 24h; the stirring speed is preferably 200-300rpm, more preferably 250-300rpm, and most preferably 250rpmn; and the stirring temperature is preferably achieved by heating.

[0047] In the present application, the rotation speed of the first centrifugation is preferably 3000-3600 rpm, more preferably 3100-3500 rpm, and most preferably 3200-3300 rpm; the time of the first centrifugation is preferably 3-5 min, more preferably 3.5-4.5 min, and most preferably 3.8-4.2 min.

[0048] After the first centrifugation is completed, the present application also preferably includes washing, which is preferably 2 times of washing with ethanol.

[0049] In the present application, the water is preferably deionized water or ultrapure water, and the ratio of the use amount of the product obtained after the first centrifugation to water is preferably 1 g:500-1000 mL, more preferably 1 g:800-1000 mL, and most preferably 1 g:1000 mL.

[0050] In the present application, the frequency of the ultrasonic is preferably 40-80 KHz, more preferably 60-80 KHz, and most preferably 60 KHz; the time of the ultrasonic is preferably 18-30 h, more preferably 24-30 h, and most preferably 24 h.

[0051] In the present 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.

[0052] After the second centrifugation is completed, the present application also preferably includes drying, and the temperature of the drying is preferably 50-65℃, more preferably 60-65℃, and most preferably 60℃; the time of the drying is preferably 10-15 h, more preferably 12-15 h, and most preferably 12 h.

[0053] In the present application, the first mixing is preferably mixing 2,5-diaminobenzenesulfonic acid and water, and then adding the MXene nanosheet; the first mixing is preferably carried out under stirring; the rotation speed of the stirring is preferably 200-300 rpm, more preferably 220-280 rpm, and most preferably 240-260 rpm; the time of the stirring is preferably 0.3 h, more preferably 1 h, and most preferably 0.5 h; and the temperature of the stirring is preferably room temperature.

[0054] In the present application, the mass ratio of the MXene nanosheet, 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.

[0055] In the present application, the modification is preferably carried out under stirring; the stirring speed is preferably 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°C, more preferably 80-85°C, and most preferably 80°C; and the stirring temperature is preferably achieved by heating through an oil bath.

[0056] After the modification is completed, the present application further preferably comprises vacuum filtration and drying, which are carried out in sequence. The process of the vacuum filtration is not particularly limited in the present application, and conventional vacuum filtration using a filter membrane well known to those skilled in the art can be used. In the present application, the drying method is preferably drying, and the drying temperature is preferably 60°C, and the drying time is preferably 12 h.

[0057] After obtaining the aminated modified MXene nanosheets, the aminated modified MXene nanosheets, water, and a tetrabutylphosphonium hydroxide benzotriazolyl lignin composite material are mixed to graft, thereby obtaining the modified MXene nanosheets.

[0058] In the present application, the water is preferably deionized water or distilled water.

[0059] In the present application, the tetrabutylphosphonium hydroxide benzotriazolyl lignin composite material is preferably prepared; and the preparation method of the tetrabutylphosphonium hydroxide benzotriazolyl lignin composite material preferably comprises the following steps:

[0060] In a 500 mL single-neck flask, 0.4 mol of benzotriazole and 0.4 mol of tetrabutylphosphonium hydroxide are added, and the reaction is carried out under nitrogen protection for 24 hours; after the reaction is completed, the water is distilled off under reduced pressure, dissolved with dichloromethane, and dried with anhydrous magnesium sulfate overnight; filtered, and the solvent is distilled off under reduced pressure to obtain a light yellow transparent oily liquid, which is an ionic liquid tetrabutylphosphonium hydroxide benzotriazolyl (marked as BTA-P 4444 ), with a yield of 95%. 5 grams of lignin are added to 95 g of BTA-P 4444 , heated to 150°C, and stirred for 10 min to obtain a tetrabutylphosphonium hydroxide benzotriazolyl lignin composite material.

[0061] In the present application, the second mixing preferably comprises adding the aminated modified MXene nanosheets and water after ultrasonic mixing, and then adding the tetrabutylphosphonium hydroxide benzotriazole lignin composite material. In the present application, the frequency of the ultrasonic mixing is preferably 40-80 KHz, more preferably 60-80 KHz, and most preferably 60 KHz; the time of the ultrasonic mixing is preferably 0.5-1.5 h, more preferably 1-1.2 h, and most preferably 1 h. The present application does not have any special limitations on the adding process of the tetrabutylphosphonium hydroxide benzotriazole lignin composite material, which can be carried out by using a process well known to those skilled in the art.

[0062] In the present application, the mass ratio of the aminated modified MXene nanosheets, water and tetrabutylphosphonium hydroxide benzotriazole lignin composite material is preferably (1-2):(1-2):(2-3), more preferably 1:1:(2-3), and most preferably 1:1:2.

[0063] In the present application, the grafting is preferably carried out under stirring, the temperature of the stirring is preferably 80-90℃, more preferably 85-90℃, and most preferably 85℃; the time of the stirring is preferably 18-24 h, more preferably 20-24 h, and most preferably 20 h; the speed of the stirring is preferably 200-300 rpm, more preferably 250-300 rpm, and most preferably 250 rpm; and the temperature of the stirring is preferably achieved by oil bath heating.

[0064] After the grafting is completed, the present application also preferably comprises vacuum filtration, washing and drying, which are carried out in sequence; the present application does not have any special limitations on the process of the vacuum filtration, which can be carried out by using a filter membrane and conventional vacuum filtration well known to those skilled in the art. In the present application, the washing is preferably carried out by using deionized water, and the present application does not have any special limitations on the number of times of the washing, which can be carried out by using a number well known to those skilled in the art. In the present application, the drying is preferably carried out by drying, and the temperature of the drying is preferably 60℃, and the time is preferably 12 h.

[0065] Based on the mass fraction of the water-based epoxy resin, the preparation raw material of the corrosion and wear resistant integrated coating of the present application comprises 20-40 parts of a curing agent, preferably 25-35 parts, and more preferably 28-32 parts. In the present application, the curing agent is preferably a triethylenetetramine curing agent.

[0066] In the present application, the role of the curing agent is to promote the drying and curing of the coating, and to enhance the adhesion between the paint film and the substrate.

[0067] The preparation raw material of the corrosion and wear resistant integrated coating of the present application includes 0.01-0.05 parts of dispersant, preferably 0.02-0.04 parts, and more preferably 0.025-0.035 parts, based on the mass fraction of the waterborne epoxy resin. In the present application, the dispersant includes one or several of BYK-104s, BYK-166 and BYK-410. When the dispersant is two or more of the above specific choices, the present application does not have any special limitation on the ratio of the above specific substances, and mixing in any ratio can be used.

[0068] In the present application, the role of the dispersant is to prevent the center of gravity of the modified MXene nanosheet from settling and maintain the suspended state of the nanosheet.

[0069] The preparation raw material of the corrosion and wear resistant integrated coating of the present application includes 0.01-0.05 parts of defoaming agent, preferably 0.02-0.04 parts, and more preferably 0.025-0.035 parts, based on the mass fraction of the waterborne epoxy resin. In the present application, the defoaming agent preferably includes one or several of silicone defoaming agent, BYK-052N and BYK-410. When the defoaming agent is two or more of the above specific choices, the present application does not have any special limitation on the ratio of the above specific substances, and mixing in any ratio can be used.

[0070] In the present application, the role of the defoaming agent is to avoid the formation of bubbles in the waterborne epoxy coating or to exclude the bubbles that have been formed in the waterborne epoxy coating.

[0071] The preparation raw material of the corrosion and wear resistant integrated coating of the present application includes 0.01-0.05 parts of leveling agent, preferably 0.02-0.04 parts, and more preferably 0.025-0.035 parts, based on the mass fraction of the waterborne epoxy resin. In the present application, the leveling agent preferably includes one or several of BYK-345, BYK-300 and BYK-370. When the leveling agent is two or more of the above specific choices, the present application does not have any special limitation on the ratio of the above specific substances, and mixing in any ratio can be used.

[0072] In the present application, the role of the leveling agent is to help form a flat, smooth and uniform coating film during the drying process of the waterborne epoxy coating.

[0073] The preparation raw material of the corrosion and wear resistant integrated coating of the present application includes 20-40 parts of solvent, preferably 25-35 parts, and more preferably 28-32 parts, based on the mass fraction of the waterborne epoxy resin. In the present application, the solvent is preferably water, and more preferably deionized water.

[0074] The application also provides a preparation method of the corrosion and wear resistant integrated coating.

[0075] The water-based epoxy resin, the modified MXene nanosheet, the curing agent, the dispersing agent, the defoaming agent, the leveling agent and the solvent are mixed to obtain a mixed slurry.

[0076] The mixed slurry is sprayed on the surface of the substrate, and is cured to obtain the corrosion and wear resistant integrated coating.

[0077] The water-based epoxy resin, the modified MXene nanosheet, the curing agent, the dispersing agent, the defoaming agent, the leveling agent and the solvent are mixed to obtain a mixed slurry.

[0078] In the application, the mixing is preferably that the water-based epoxy resin, the modified MXene nanosheet, the dispersing agent, the defoaming agent, the leveling agent and the solvent are mixed to obtain a mixed liquid, and the mixed liquid and the curing agent are mixed. In the application, the mixing of the water-based epoxy resin, the modified MXene nanosheet, the dispersing agent, the defoaming agent, the leveling agent and the solvent is preferably carried out under stirring, and the stirring speed is preferably 300-400 rpm, preferably 320-380 rpm, and more preferably 340-360 rpm. The stirring time is preferably 25-35 min, more preferably 30-32 min, and most preferably 30 min. In the application, the mixing of the slurry and the curing agent is preferably carried out under stirring. The stirring speed is preferably 200-300 rpm, more preferably 220-280 rpm, and most preferably 240-260 rpm. The time is preferably 4-7 min, more preferably 5-7 min, and most preferably 5 min.

[0079] After obtaining the mixed slurry, the mixed slurry is sprayed on the surface of the substrate, and is cured to obtain the corrosion and wear resistant integrated coating.

[0080] In the application, the substrate is preferably a substrate treated according to the national standard GB / T8923.1

[0081] In the application, the spraying condition is preferably that the distance between the mixed slurry and the surface of the substrate is preferably 20-25 cm, more preferably 21-24 cm, and most preferably 22-23 cm. The spraying is preferably carried out in compressed air with a pressure of 0.15-0.25 MPa.

[0082] In the application, the curing temperature is preferably room temperature, and the curing time is preferably 24 h.

[0083] In the application, the thickness of the corrosion and wear resistant integrated coating is preferably 50-70 μm, more preferably 55-65 μm, and most preferably 58-62 μm.

[0084] The application also provides application of the corrosion and wear resistant integrated coating prepared by the preparation method in the field of marine corrosion prevention. In the application, the application is preferably application in a submarine propeller shaft sleeve or a metal driving part of a sea oil extraction platform. The application does not have any special limitation on the method of the application, and the method known to those skilled in the art can be used.

[0085] The corrosion and wear resistant integrated coating provided by the application, the preparation method and the application thereof are described in detail below in combination with examples, but they should not be understood as limitations on the protection scope of the application.

[0086] Preparation method of modified MXene nanosheet:

[0087] 1g of Ti3C2 MXene (particle size of 300 mesh) and 150mL of dimethyl sulfoxide (DMSO) were added into a round-bottom flask for mixing, and constant temperature stirring was carried out in an oil bath at 60°C for 24 hours. The obtained mixture was separated by a centrifuge (at a speed of 3200rpm for 4min), washed with ethanol for 2 times, 0.5g of the centrifuged nanosheet was added into 500mL of deionized water, and ultrasonic dispersion was carried out for 24h (at a frequency of 60KHz), then centrifugation was carried out (at a speed of 9000rpm for 10min), and 60°C oven drying was carried out for 12h to obtain the pretreated MXene.

[0088] 0.2g of 2,5-diaminobenzenesulfonic acid was dissolved in 200mL of ultrapure water to prepare a mixed solution, and then 0.4g of the nanosheet was added. Intensive stirring was carried out at room temperature for 0.5h (at a speed of 250rmp), so that the nanosheet was completely dispersed. Then, intensive stirring was carried out at 80°C for 2h, vacuum filtration was carried out by using a filter membrane, and 60°C oven drying was carried out for 12h to obtain the amino-modified MXene nanosheet (f-MXene).

[0089] 0.2g of the amino-modified MXene was dissolved in 200mL of deionized water and ultrasonically dispersed for 1h (at a frequency of 60KHz), and then 0.4g of tetrabutylphosphonium hydroxide benzotriazole lignin composite (BTA-P 444 -Lig) was added. Heating was carried out to 90°C, and continuous stirring was carried out for 20h (at a speed of 250rmp). Vacuum filtration was carried out by using a filter membrane, deionized water was used for washing for several times, and 60°C oven drying was carried out for 12h to obtain the modified MXene nanosheet (f-MXene-P).

[0090] Example 1

[0091] Preparation of the corrosion and wear resistant integrated coating: water-based epoxy resin 30 parts, modified MXene nanosheet (f-MXene-P) 0.22 parts, dispersing agent (specific type is BYK-104s) 0.03 parts, defoaming agent (specific type is silicone defoaming agent) 0.03 parts, leveling agent (specific type is BYK-345) 0.03 parts, deionized water 30 parts, curing agent (specific type is triethylenetetramine curing agent) 30 parts;

[0092] Preparation method of the corrosion and wear resistant integrated coating:

[0093] Mix the water-based epoxy resin, f-MXene-P nanosheet, dispersing agent, defoaming agent, leveling agent and solvent (rotation speed is 400 rpm, time is 30 min) to obtain a mixed solution; mix the mixed solution and the curing agent (rotation speed is 300 rpm, time is 5 min) to obtain a mixed slurry;

[0094] Spray the mixed slurry on the surface of a substrate (Q235 steel) treated according to national standard GB / T 8923.1 (the distance between the mixed slurry and the surface of the substrate is 20 cm; the spraying is performed in compressed air at 0.15 MPa), and cure at room temperature for 24 h to obtain the corrosion and wear resistant integrated coating.

[0095] Example 2

[0096] Preparation of the corrosion and wear resistant integrated coating: water-based epoxy resin 40 parts, modified MXene nanosheet (f-MXene-P) 0.5 parts, dispersing agent (specific type is BYK-104s) 0.03 parts, defoaming agent (specific type is silicone defoaming agent) 0.03 parts, leveling agent (specific type is BYK-345) 0.03 parts, deionized water 30 parts, curing agent (specific type is triethylenetetramine curing agent) 40 parts;

[0097] Preparation method of the corrosion and wear resistant integrated coating:

[0098] Mix the water-based epoxy resin, f-MXene-P nanosheet, dispersing agent, defoaming agent, leveling agent and solvent (rotation speed is 400 rpm, time is 30 min) to obtain a mixed solution; mix the mixed solution and the curing agent (rotation speed is 300 rpm, time is 5 min) to obtain a mixed slurry;

[0099] Spray the mixed slurry on the surface of a substrate (Q235 steel) treated according to national standard GB / T 8923.1 (the distance between the mixed slurry and the surface of the substrate is 25 cm; the spraying is performed in compressed air at 0.15 MPa), and cure at room temperature for 24 h to obtain the corrosion and wear resistant integrated coating.

[0100] Example 3

[0101] The preparation raw materials (by mass fraction) of the corrosion and wear resistant integrated coating are as follows: 20 parts of water-based epoxy resin, 0.1 part of modified MXene nanosheet (f-MXene-P), 0.02 part of dispersant (the specific type is BYK-104s), 0.02 part of defoaming agent (the specific type is silicone defoaming agent), 0.02 part of leveling agent (the specific type is BYK-345), 20 parts of deionized water, and 20 parts of curing agent (the specific type is triethylenetetramine curing agent).

[0102] The preparation method of the corrosion and wear resistant integrated coating is as follows:

[0103] The water-based epoxy resin, f-MXene-P nanosheet, dispersant, defoaming agent, leveling agent, and solvent are mixed (at a rotation speed of 350 rpm for 30 min) to obtain a mixed solution; and the mixed solution and the curing agent are mixed (at a rotation speed of 300 rpm for 5 min) to obtain a mixed slurry.

[0104] The mixed slurry is sprayed on the surface of a substrate (Q235 steel) treated according to the national standard GB / T 8923.1 (the distance between the mixed slurry and the surface of the substrate is 23 cm; the spraying is performed in compressed air at a pressure of 0.15 MPa), and is cured at room temperature for 24 h to obtain the corrosion and wear resistant integrated coating (the physical map is shown in FIG. 1). Figure 1

[0105] Comparative Example 1

[0106] The water-based epoxy resin (the specific type is bisphenol A type water-based epoxy resin) 20 parts, the dispersant (the specific type is BYK-104s) 0.05 parts, the defoaming agent (the specific type is silicone defoaming agent) 0.05 parts, the leveling agent (the specific type is BYK-345) 0.05 parts, and the solvent (the specific type is deionized water) 20 parts are configured into a mixed slurry and mixed at a rotation speed of 300 rpm for 30 min; 20 parts of curing agent (the specific type is triethylenetetramine curing agent) is added to the mixed solution and mixed at a rotation speed of 300 rpm for 5 min. Finally, the water-based epoxy corrosion and wear resistant integrated coating is sprayed on the surface of a substrate (Q235 steel) treated according to the national standard GB / T 8923.1, and is cured at room temperature for 24 h to obtain a water-based epoxy coating (WEP).

[0107] Comparative Example 2

[0108] ​The water-based epoxy resin (specific type: bisphenol A type water-based epoxy resin) 20 parts, MXene nanosheet 0.1 part, dispersing agent (specific type: BYK-104s) 0.05 part, defoaming agent (specific type: silicone defoaming agent) 0.05 part, leveling agent (specific type: BYK-345) 0.05 part and solvent (specific type: deionized water) 20 parts are configured into a mixed slurry and mixed at a speed of 300 rpm for 30 min; 20 parts of curing agent (specific type: triethylene tetramine curing agent) are added to the mixed slurry and mixed at a speed of 300 rpm for 5 min. Finally, the water-based epoxy corrosion and wear-resistant integrated coating (MXene / WEP) is obtained by spraying the water-based epoxy corrosion and wear-resistant integrated coating on the surface of the substrate (Q235 steel) treated according to the national standard GB / T 8923.1 and curing at room temperature for 24 h.

[0109] Comparative Example 3

[0110] The water-based epoxy resin (specific type: bisphenol A type water-based epoxy resin) 20 parts, MXene nanosheet 0.1 part, dispersing agent (specific type: BYK-104s) 0.05 part, defoaming agent (specific type: silicone defoaming agent) 0.05 part, leveling agent (specific type: BYK-345) 0.05 part and solvent (specific type: deionized water) 20 parts are configured into a mixed slurry and mixed at a speed of 300 rpm for 30 min; 20 parts of curing agent (specific type: triethylene tetramine curing agent) are added to the mixed slurry and mixed at a speed of 300 rpm for 5 min. Finally, the water-based epoxy corrosion and wear-resistant integrated coating (MXene / WEP) is obtained by spraying the water-based epoxy corrosion and wear-resistant integrated coating on the surface of the substrate (Q235 steel) treated according to the national standard GB / T 8923.1 and curing at room temperature for 24 h.

[0111] Figure 2 The corrosion resistance of the corrosion and wear-resistant integrated coating described in Comparative Example 1, Comparative Example 2, Comparative Example 3 and Example 3 is tested by Figure 2 It can be seen that the corrosion resistance of the water-based epoxy composite coating (f-MXene-P / WEP) modified by the MXene (f-MXene-P) modified by the tetrabutylphosphonium hydroxide benzotriazole lignin composite material is greatly improved compared with the water-based epoxy coating (WEP), and the addition of f-MXene-P improves the corrosion resistance of the water-based epoxy coating;

[0112] Figure 3 The wear resistance of the corrosion and wear-resistant integrated coating described in Comparative Example 1, Comparative Example 2, Comparative Example 3 and Example 3 is tested by Figure 3It can be seen that the f-MXene-P / WEP composite coating has the smallest friction coefficient, and the addition of f-MXene-P greatly improves the wear resistance of the water-based epoxy coating.

[0113] Figure 4 For the wear morphology (SEM image) of the anti-corrosion and wear-resistant integrated coating of Comparative Example 1, Comparative Example 2, Comparative Example 3 and Example 3, (a), (a1), (b), (b1), (c), (c1) are the wear morphology of Comparative Example 1 (WEP) under scanning electron microscope magnification of 200 times, the wear morphology of Comparative Example 1 (WEP) under scanning electron microscope magnification of 1000 times, the wear morphology of Comparative Example 2 (MXene / WEP) under scanning electron microscope magnification of 200 times, the wear morphology of Comparative Example 2 (MXene / WEP) under scanning electron microscope magnification of 1000 times, the wear morphology of Comparative Example 3 (f-MXene / WEP) under scanning electron microscope magnification of 200 times and the wear morphology of Comparative Example 3 (f-MXene / WEP) under scanning electron microscope magnification of 1000 times, respectively; (d), (d1) are the wear morphology of Example 3 (f-MXene-P / WEP) under scanning electron microscope magnification of 200 times and 1000 times, respectively. Figure 4 It can be seen that the wear track of the f-MXene-P / WEP composite coating is the shallowest, and the wear resistance is greatly improved compared with the WEP coating.

[0114] The detection method and performance data of the anti-corrosion and wear-resistant integrated coating of Examples 1-3 and the anti-corrosion and wear-resistant integrated coating of Comparative Examples 1-3 are shown in Table 1.

[0115] Table 1 Detection method and performance data of the anti-corrosion and wear-resistant integrated coating of Examples 1-3 and Comparative Examples 1-3

[0116]

[0117] As can be seen from Table 1, the anti-corrosion and wear-resistant integrated coating has a low friction coefficient and excellent corrosion resistance, and can be exposed to marine environment for long-term use.

[0118] The above is only the preferred embodiment of the present application, and it should be pointed out that for ordinary skilled in the art, without departing from the principles of the present application, a number of improvements and refinements can be made, which should be considered as the protection scope of the present application.

Claims

1. A corrosion and wear resistant integrated coating, characterized in that, According to the mass fraction, the following preparation raw materials are included: 20-40 parts of water-based epoxy resin, 0.1-0.5 parts of modified MXene nanosheet, 20-40 parts of curing agent, 0.01-0.05 parts of dispersing agent, 0.01-0.05 parts of defoaming agent, 0.01-0.05 parts of leveling agent, and 20-40 parts of solvent; The modified MXene nanosheet is a MXene nanosheet grafted with tetrabutylphosphonium hydroxide benzotriazole lignin composite material; The preparation method of the modified MXene nanosheet comprises the following steps: The MXene nanosheet, 2,5-diamino benzene sulfonic acid, and water are first mixed for modification to obtain the amino-modified MXene nanosheet; The amino-modified MXene nanosheet, water, and tetrabutylphosphonium hydroxide benzotriazole lignin composite material are secondly mixed for grafting to obtain the modified MXene nanosheet; Before the first mixing, the MXene nanosheet is pretreated; The pretreatment comprises the following steps: After the MXene and dimethyl sulfoxide are mixed, the nanosheet and water centrifuged out are mixed, and ultrasonic and second centrifugation are sequentially performed to obtain the pretreated MXene nanosheet; The mass ratio of the MXene nanosheet, 2,5-diamino benzene sulfonic acid, and water is (1-2):(1-2):1; The modification is performed under stirring, the stirring temperature is 75-85°C, the stirring speed is 200-300 rpm, and the stirring time is 2-3 h; The mass ratio of the amino-modified MXene nanosheet, water, and tetrabutylphosphonium hydroxide benzotriazole lignin composite material is (1-2):(1-2):(2-3); The grafting is performed under stirring, the stirring temperature is 80-90°C, the stirring speed is 200-300 rpm, and the stirring time is 18-24 h.

2. The corrosion and wear resistant integrated coating of claim 1, wherein, The water-based epoxy resin is a bisphenol A type water-based epoxy resin, and the epoxy value of the water-based epoxy resin is 0.55-0.

6.

3. The corrosion and wear resistant integrated coating of claim 1, wherein, The curing agent is a triethylene tetramine curing agent; The dispersing agent includes one or more of BYK-104s, BYK-166, and BYK-410.

4. The corrosion and wear resistant integrated coating of claim 1, wherein, The defoaming agent includes one or more of silicone defoaming agent, BYK-052N, and BYK-410; The leveling agent includes one or more of BYK-345, BYK-300, and BYK-370; The solvent is water.

5. Process for the production of the anticorrosion-wear resistant integrated coating according to any one of claims 1 to 4, characterized in that, The preparation method comprises the following steps: The water-based epoxy resin, modified MXene nanosheet, curing agent, dispersing agent, defoaming agent, leveling agent, and solvent are mixed to obtain a mixed slurry; The mixed slurry is sprayed on the surface of a substrate, and cured to obtain the corrosion and wear resistant integrated coating.

6. Application of the corrosion and wear resistant integrated coating of any one of claims 1-4 or prepared by the preparation method of claim 5 in the field of marine corrosion prevention.

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