MXene-based deicing super-hydrophobic paint, coating, preparation method and application of coating

Abstract

The invention relates to a deicing super-hydrophobic coating based on MXene, a coating, a preparation method and application of the coating. The coating comprises the following components in percentage by mass: 2%-5% of a super-hydrophobic modified MXene photo-thermal material, 2%-5% of epoxy resin, 0.5%-1.5% of an epoxy resin curing agent, 0.5%-1.5% of PDMS, 0.05%-0.15% of a PDMS curing agent and 80%-90% of a diluent. Wherein the super-hydrophobic modified MXene photo-thermal material is MXene powder treated by fluorine-free long-chain silane, and the super-hydrophobic modified MXene photo-thermal material is a super-hydrophobic modified MXene photo-thermal material. MXene with excellent photo-thermal conversion performance is used as a photo-thermal material, fluorine-free long-chain silane is used for performing low-surface-energy hydrophobic modification on the MXene material, environmental pollution caused by perfluorinated or polyfluorinated organic compounds is avoided, photo-thermal performance and super-hydrophobic performance are integrated, the advantages of a super-hydrophobic coating and a photo-thermal coating are integrated, and the application prospect is wide. The deicing super-hydrophobic coating based on MXene can be used for passive ice prevention and active photo-thermal deicing.

Description

Technical Field

[0001] The present invention relates to the technical field of anti-icing and de-icing of superhydrophobic coatings, and specifically relates to an MXene-based de-icing superhydrophobic coating, coating preparation method and application thereof. Background Art

[0002] Icing is a common and inevitable phenomenon in nature. However, for outdoor equipment or devices such as highways, power lines and wind power generation equipment, surface icing brings significant safety challenges and economic losses. In the past few decades, many anti-icing / de-icing strategies have been attempted, such as electrothermal or steam heating for ice melting, chemical de-icing and mechanical vibration de-icing. However, these methods usually have high energy consumption, low cost-effectiveness or are harmful to the environment, and cannot meet the growing requirements for low carbon emissions and ecosystem protection.

[0003] In recent years, passive anti-icing technology has received increasing attention as an effective anti-icing strategy. Passive anti-icing technology aims to reduce surface icing and relies only on the superhydrophobic or anti-icing properties inside the material to reduce external intervention and thus save costs. For example, superhydrophobic coatings (SHCs) with excellent water repellency inspired by lotus leaves and slippery liquid-infused porous surfaces (SLIPS) inspired by Nepenthes. These two technologies not only have good anti-icing and icing delay performance, but also have low energy consumption and are environmentally friendly. However, the lubricant in SLIPS will be lost over time, resulting in the loss of anti-icing performance of SLIPS, which is not suitable for long-term practical applications. Superhydrophobic coatings mainly reduce the contact area and contact time between water droplets and the surface through the synergistic effect of micro-nano structures and low surface energy, greatly extending the icing time, and thus have excellent passive anti-icing ability. However, the micro-nano structures on the superhydrophobic surface are very fragile, which may lead to a reduction in the long-term anti-icing ability of the surface. More importantly, the icing behavior in a low-temperature and high-humidity environment may lead to mechanical interlocking between ice and the surface micro-nano structures and a significant increase in ice adhesion strength, thereby depriving the surface of its anti-icing ability. Therefore, there is an urgent need to find a more efficient and durable de-icing strategy.

[0004] Therefore, there is provided an MXene-based de-icing superhydrophobic coating, coating preparation method and coating application that have better performance and can both passively prevent icing and actively de-ice by photothermal effect. Summary of the Invention

[0005] Aiming at the problems of difficult de-icing, low efficiency and high cost of outdoor devices in the prior art, the present invention provides an MXene-based de-icing superhydrophobic coating, coating preparation method and coating application that have better performance and can both passively prevent icing and actively de-ice by photothermal effect.

[0006] First, the present invention provides an anti-icing superhydrophobic coating based on MXene, comprising the following components in mass percentages: 2% - 5% of superhydrophobic modified MXene photothermal material, 2% - 5% of epoxy resin, 0.5% - 1.5% of epoxy resin curing agent, 0.5% - 1.5% of PDMS, 0.05% - 0.15% of PDMS curing agent, and 80% - 90% of diluent; Among them, the superhydrophobic modified MXene photothermal material is MXene powder treated with fluorine-free long-chain silane; The epoxy resin is one of epoxy resin E-44, E-51, E-20, and E-42; The epoxy resin curing agent is one of 593 curing agent, polyetheramine 230 curing agent, and T-31 curing agent; The PDMS and the PDMS curing agent are Dow Corning DC184 main agent and the corresponding curing agent; The diluent is one or more of ethyl acetate, butyl acetate, toluene, acetone, and n-hexane.

[0007] The fluorine-free long-chain silane includes cetyltrimethoxysilane, octadecyltrimethoxysilane, or dodecyltrimethoxysilane.

[0008] Secondly, the present invention also provides a preparation method of an anti-icing superhydrophobic coating based on MXene, comprising the following steps: S1 Preparation of MXene After mixing concentrated HCl with water to form a hydrochloric acid solution, add LiF to the hydrochloric acid solution and stir to mix, and then slowly add Ti 3 AlC 2 slowly into the above-mentioned mixed solution, seal the container and place it in a water bath at 35 - 45 °C and stir for 18 - 36 h.

[0009] Centrifuge and wash the above reaction mixture with ultrapure water until the pH of the supernatant is ≥ 6, collect the precipitate and disperse it in ultrapure water, and then ultrasonicate for 1 - 2 h under ice-water bath conditions to obtain an MXene suspension, Centrifuge the above suspension to obtain an MXene colloid, and vacuum freeze-dry for 24 - 48 h to obtain MXene powder; S2 Preparation of superhydrophobic modified MXene photothermal material Add the MXene powder prepared in S1 to an ethanol solution containing fluorine-free long-chain silane, stir and react at room temperature for 12 - 24 h, after centrifugation, remove the supernatant and vacuum freeze-dry for 24 - 48 h to obtain a superhydrophobic modified MXene photothermal material; S3 Preparation of anti-icing superhydrophobic coating based on MXene Divide the diluent into two equal parts. Add the superhydrophobic modified MXene photothermal material prepared in S2 to one part of the diluent and stir until evenly dispersed. Add epoxy resin and PDMS to the other part of the diluent and stir until evenly dispersed. After mixing the two parts of the diluent, add epoxy resin curing agent and PDMS curing agent and stir evenly again to obtain an MXene-based anti-icing superhydrophobic coating. Among them, the mass percentages of each component are: 2% - 5% of the superhydrophobic modified MXene photothermal material, 2% - 5% of the epoxy resin, 0.5% - 1.5% of the epoxy resin curing agent, 0.5% - 1.5% of the PDMS, 0.05% - 0.15% of the PDMS curing agent, and 80% - 90% of the diluent.

[0010] In S1, the concentration of the hydrochloric acid solution is 9 mol / L, and the mass ratio of LiF to Ti 3 AlC 2 is (1 - 1.6):1.

[0011] In S2, the mass ratio among the MXene powder, the long-chain silane and the diluent is (1 - 2):(1 - 2):50.

[0012] The epoxy resin is one of epoxy resin E-44, E-51, E-20, and E-42; The epoxy resin curing agent is one of 593 curing agent, polyetheramine 230 curing agent, and T-31 curing agent; The PDMS and the PDMS curing agent are Dow Corning DC184 main agent and the corresponding curing agent; The diluent is one or more of ethyl acetate, butyl acetate, toluene, acetone, and n-hexane, The fluorine-free long-chain silane includes hexadecyltrimethoxysilane, octadecyltrimethoxysilane, or dodecyltrimethoxysilane.

[0013] Furthermore, the present invention also provides an MXene-based anti-icing superhydrophobic coating, which is prepared by using the above-mentioned MXene-based anti-icing superhydrophobic coating material.

[0014] Furthermore, the present invention also provides a method for preparing an MXene-based anti-icing superhydrophobic coating. Spray the prepared superhydrophobic coating material on the substrate by spraying method, and obtain an MXene-based anti-icing superhydrophobic coating with passive anti-icing and active photothermal anti-icing after curing at a constant temperature.

[0015] Pretreat the substrate before spraying: sand the substrate with sandpaper, and then perform ultrasonic cleaning using ethanol and ultrapure water; during spraying, the spraying pressure of the spray gun is 2 bar to 4 bar, the nozzle diameter of the spray gun is 0.3 to 0.8 mm, and the distance between the nozzle and the substrate is 15 to 20 cm.

[0016] Finally, the present invention provides an application of an anti-icing superhydrophobic coating based on MXene, and applies the anti-icing superhydrophobic coating based on MXene as described above to the fields of aerospace, wind power generation, wire and cable, or other power facilities.

[0017] The technical solution of the present invention has the following advantages: 1. In the present invention, MXene is used as a photothermal material, which has excellent photothermal conversion performance. The MXene material is modified with a fluorine-free long-chain silane to have low surface energy and hydrophobicity, avoiding the environmental pollution caused by perfluoro- or polyfluoro-organic compounds. At the same time, the photothermal performance and superhydrophobic performance are integrated, simplifying the process flow, integrating the advantages of superhydrophobic coatings and photothermal coatings, and being energy-saving and environmentally friendly compared with traditional anti-icing technologies.

[0018] 2. The present invention uses epoxy resin as an adhesive to firmly attach the superhydrophobically modified MXene photothermal material to the substrate, and uses PDMS as an auxiliary adhesive to simultaneously reduce the surface energy of the coating, achieve long-term maintenance of superhydrophobicity, and form an epoxy-PDMS dynamic bonding network to avoid the functional limitations of a single adhesive; during use, through particle size control and spraying parameter adjustment, uniform coating of the coating is achieved, and the operation is simple, suitable for various substrates such as metals, glasses, and composite materials.

[0019] 3. The anti-icing superhydrophobic coating based on MXene prepared by the present invention has good passive anti-icing and photothermal active anti-icing performance, can effectively delay the icing time in a low-temperature and dark environment of -10°C and -20°C, and the icing time will be further extended under light conditions; the results of photothermal heating experiments and photothermal anti-icing experiments show that under a solar irradiance of 100 mW / cm 2 ) the surface temperature of the coating rises rapidly, and the frost layer and ice layer on the coating surface can melt rapidly, and even under lower ambient temperatures and weaker light intensities, the coating still has good anti-icing and de-icing performance.

[0020] 4. The anti-icing superhydrophobic coating based on MXene prepared by the present invention has excellent chemical stability and mechanical durability, and can still maintain superhydrophobic performance under conditions such as repeated tape peeling, cyclic sandpaper abrasion, water jet impact, sand and gravel impact, strong acid and alkali / corrosion, etc., and is suitable for applications in harsh environments.

[0021] 5. The preparation method of the MXene-based anti-icing superhydrophobic coating provided by the present invention uses a fluorine-free long-chain silane to modify MXene to achieve the integration of photothermal and superhydrophobic properties. The method has simple and controllable process and low cost, laying a technical foundation for large-scale industrial production and commercial promotion. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following will briefly introduce the drawings required for the description of the specific embodiments or the prior art. Obviously, the drawings in the following description are an application mode of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on this drawing.

[0023] Figure 1 It is the water contact angle diagram of the MXene-based anti-icing superhydrophobic coating described in Example 1 of the present invention and the blank aluminum plate in Comparative Example 1, where (a) is the water contact angle of the blank aluminum plate, and (b) is the water contact angle of the MXene-based anti-icing superhydrophobic coating; Figure 2 It is the heating curve of the MXene-based anti-icing superhydrophobic coating described in Example 1 of the present invention, Example 8, Example 9 and the blank aluminum plate in Comparative Example 1 under the light intensity condition of 100 mW / cm 2 light intensity condition; Figure 3 It is the temperature rise and fall curve of the MXene-based anti-icing superhydrophobic coating described in Example 1 of the present invention during 10 times of photothermal heating / cooling cycle tests; Figure 4 It is the comparison diagram of the ice formation start and end of the MXene-based anti-icing superhydrophobic coating described in Example 1 of the present invention and the blank aluminum plate in Comparative Example 1 under the condition of -20°C; Figure 5 It is the comparison diagram of the start and end of ice droplet melting of the MXene-based anti-icing superhydrophobic coating described in Example 1 of the present invention and the blank aluminum plate in Comparative Example 1 under the conditions of -20°C and 100 mW / cm 2 light intensity condition; Figure 6 It is the comparison diagram of the start and end of ice layer melting of the MXene-based anti-icing superhydrophobic coating described in Example 1 of the present invention and the blank aluminum plate in Comparative Example 1 under the conditions of -20°C and 100 mW / cm 2 light intensity condition; Figure 7 It is the comparison diagram of the start and end of frost layer melting of the MXene-based anti-icing superhydrophobic coating described in Example 1 of the present invention and the blank aluminum plate in Comparative Example 1 under the conditions of -20°C and 100 mW / cm 2 light intensity condition; Figure 8 The contact angle change diagram during the 200 - time wear test (each wear distance is 10 cm) under a 50 - g load on 800 - mesh sandpaper for the MXene - based anti - icing super - hydrophobic coating obtained in Example 1 of the present invention; Figure 9 For the MXene - based anti - icing super - hydrophobic coating cable and the blank cable of the present invention at - 20°C and 100 mW / cm 2 The comparison diagram of the start and end of surface ice layer melting in 10 min under the light intensity condition. Detailed implementation manners

[0024] In order to further elaborate the purpose, technical solutions and advantages of the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be described in detail below. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of them. Based on these embodiments of the present invention, all other embodiments obtained without creative labor belong to the protection scope of the present invention.

[0025] For the materials, reagents, etc. used in the present invention, unless otherwise specified, the actual and materials used in the following embodiments are considered to be obtainable from commercial channels.

[0026] First, the present invention provides a MXene - based anti - icing super - hydrophobic coating, comprising the following components in mass percentages: 2% - 5% of super - hydrophobic modified MXene photothermal material, 2% - 5% of epoxy resin, 0.5% - 1.5% of epoxy resin curing agent, 0.5% - 1.5% of PDMS, 0.05% - 0.15% of PDMS curing agent, and 80% - 90% of diluent; Among them, the super - hydrophobic modified MXene photothermal material is MXene powder treated with fluorine - free long - chain silane; The epoxy resin is one of epoxy resin E - 44, E - 51, E - 20, E - 42; The epoxy resin curing agent is one of 593 curing agent, polyetheramine 230 curing agent, T - 31 curing agent; The PDMS and the PDMS curing agent are Dow Corning DC184 main agent and the corresponding curing agent; The diluent is one or more of ethyl acetate, butyl acetate, toluene, acetone, n - hexane.

[0027] The fluorine - free long - chain silane includes hexadecyltrimethoxysilane, octadecyltrimethoxysilane or dodecyltrimethoxysilane.

[0028] Secondly, the present invention also provides a preparation method of a MXene - based anti - icing super - hydrophobic coating, comprising the following steps: S1 Prepare MXene After mixing concentrated HCl with water to form a hydrochloric acid solution, LiF is added to the hydrochloric acid solution and stirred for 30 min, and then Ti 3 AlC 2 is slowly added to the above-mentioned mixture. After sealing the container, it is placed in a water bath at 35 °C and stirred for 18 - 36 h.

[0029] The above reaction mixture is centrifugally washed with ultrapure water at a rotation speed of 3500 r / min until the pH of the supernatant is ≥ 6. The precipitate is collected and dispersed in ultrapure water, and then ultrasonicated for 1 h under ice-water bath conditions to obtain a MXene suspension. After centrifuging the above suspension at a rotation speed of 5000 r / min for 30 min, a MXene colloid is obtained, and vacuum freeze-dried for 48 h to obtain MXene powder. S2 Preparation of superhydrophobic modified MXene photothermal material The MXene powder prepared in S1 is added to an ethanol solution containing fluorine-free long-chain silane, and stirred at room temperature for 24 h. After centrifuging at a rotation speed of 5000 r / min for 10 min, the supernatant is removed and vacuum freeze-dried for 24 h to obtain a superhydrophobic modified MXene photothermal material. S3 Preparation of MXene-based ice-removing superhydrophobic coating The diluent is divided into two equal parts. The superhydrophobic modified MXene photothermal material prepared in S2 is added to one part of the diluent and stirred for 30 min until evenly dispersed; epoxy resin and PDMS are added to the other part of the diluent and stirred for 10 min until evenly dispersed; after mixing the two parts of the diluent, an epoxy resin curing agent and a PDMS curing agent are added, and stirred evenly again to obtain a MXene-based ice-removing superhydrophobic coating. Among them, the mass percentages of each component are: superhydrophobic modified MXene photothermal material 2% - 5%, epoxy resin 2% - 5%, epoxy resin curing agent 0.5% - 1.5%, PDMS 0.5% - 1.5%, PDMS curing agent 0.05% - 0.15%, diluent 80% - 90%.

[0030] In S1, the concentration of the hydrochloric acid solution is 9 mol / L, and the mass ratio of LiF to Ti 3 AlC 2 is (1 - 1.6):1.

[0031] In S2, the mass ratio among the MXene powder, long-chain silane and diluent is (1 - 2):(1 - 2):50.

[0032] The epoxy resin is one of epoxy resin E-44, E-51, E-20, E-42; The epoxy resin curing agent is one of 593 curing agent, polyetheramine 230 curing agent, and T-31 curing agent; The PDMS and the PDMS curing agent are Dow Corning DC184 main agent and the corresponding curing agent; The diluent is one or more of ethyl acetate, butyl acetate, toluene, acetone, and n-hexane, The fluorine-free long-chain silane includes hexadecyltrimethoxysilane, octadecyltrimethoxysilane, or dodecyltrimethoxysilane.

[0033] Again, the present invention also provides an anti-icing superhydrophobic coating based on MXene, which is prepared by using the anti-icing superhydrophobic coating material based on MXene as described above.

[0034] Furthermore, the present invention also provides a method for preparing an anti-icing superhydrophobic coating based on MXene. The superhydrophobic coating material prepared is sprayed on a substrate by a spraying method, and then cured in an oven at 60 °C for 3 h to obtain the anti-icing superhydrophobic coating based on MXene.

[0035] Before spraying, the substrate is pretreated: the substrate is polished with sandpaper, and then ultrasonically cleaned with ethanol and ultrapure water; during spraying, the spraying pressure of the spray gun is 2 bar to 4 bar, the nozzle diameter of the spray gun is 0.5 mm, and the distance between the nozzle and the substrate is 15 - 20 cm.

[0036] Finally, the present invention provides an application of the anti-icing superhydrophobic coating based on MXene, and the anti-icing superhydrophobic coating based on MXene as described above is applied to the fields of aerospace, wind power generation, wire and cable, or other power facilities.

[0037] Example 1: This example relates to a specific preparation process of an anti-icing superhydrophobic coating based on MXene, as follows: S1: Mix 45 ml of concentrated HCl with a concentration of 12 mol / L and 15 ml of ultrapure water to form a 9 mol / L hydrochloric acid solution, then add 4.8 g of LiF to the hydrochloric acid solution and stir for 30 min; Then add 3.0 g of Ti 3 AlC 2 Slowly add it to the above etching solution, and control the addition speed at 1.0 g / min; then seal the container and place it in a 35 °C water bath and stir for 24 h; The above reaction mixture was centrifugally washed with ultrapure water until the pH of the supernatant was ≥6; the precipitate was collected, dispersed in ultrapure water, and then sonicated in an ice-water bath for 1 h to obtain an MXene suspension; the above suspension was centrifuged at 3500 r / min for 30 min to obtain an MXene colloid, which was further freeze-dried under vacuum for 48 h to obtain MXene powder; S2: 2.0 g of the MXene powder prepared in S1 was added to a 50 ml ethanol solution containing 1.0 g of cetyltrimethoxysilane, and the mixture was stirred at room temperature for 24 h; after the mixture was centrifuged at 5000 r / min for 10 min, the supernatant was removed and freeze-dried under vacuum for 24 h to obtain a superhydrophobic modified MXene photothermal material; S3: 0.4 g of the superhydrophobic modified MXene photothermal material prepared in S2 was added to 5 ml of ethyl acetate and stirred for 30 min until evenly dispersed. Then, 0.4 g of epoxy resin and 0.1 g of PDMS were added to another 5 ml of ethyl acetate and stirred for 10 min until evenly dispersed; then the two dilutions were mixed, and 0.1 g of 593 epoxy resin curing agent and 0.01 g of PDMS curing agent were added and stirred for 10 min until homogeneous to obtain an ice-removing superhydrophobic coating based on MXene; S4: The ice-removing superhydrophobic coating based on MXene obtained in S3 was sprayed on an aluminum plate by spraying method and cured in an oven at 60°C for 3 h to obtain an ice-removing superhydrophobic coating based on MXene.

[0038] Example 2: This example provides a coating, which is different from Example 1 in that the addition amount of LiF described in S2 is 3.0 g, and the other components and their amounts are the same as those in Example 1.

[0039] Example 3: This example provides a coating, which is different from Example 1 in that the addition amount of LiF described in S2 is 3.9 g, and the other components and their amounts are the same as those in Example 1.

[0040] Example 4: This example provides a coating, which is different from Example 1 in that the fluorine-free long-chain silane described in S2 is octadecyltrimethoxysilane, and the other components and their amounts are the same as those in Example 1.

[0041] Example 5: This example provides a coating, which is different from Example 1 in that the fluorine-free long-chain silane described in S2 is dodecyltrimethoxysilane, and the other components and their amounts are the same as those in Example 1.

[0042] Example 6: A coating is provided in this example. The difference from Example 1 is that the addition amount of cetyltrimethoxysilane described in S2 is 0.5 g, and the other components and their amounts are the same as those in Example 1.

[0043] Example 7: A coating is provided in this example. The difference from Example 1 is that the addition amount of cetyltrimethoxysilane used in S2 is 2.0 g, and the other components and their amounts are the same as those in Example 1.

[0044] Example 8: A coating is provided in this example. The difference from Example 1 is that the addition amount of the superhydrophobic modified MXene photothermal material described in S3 is 0.2 g, and the other components and their amounts are the same as those in Example 1.

[0045] Example 9: A coating is provided in this example. The difference from Example 1 is that the addition amount of the superhydrophobic modified MXene photothermal material described in S3 is 0.6 g, and the other components and their amounts are the same as those in Example 1.

[0046] Comparative Example 1: This comparative example is a blank comparative example. The blank aluminum plate substrate is pretreated, that is, the blank aluminum plate substrate is polished with 800-mesh sandpaper, and then ultrasonically cleaned with ethanol and ultrapure water for 5 min and dried to be used as the blank comparative example.

[0047] Comparative Example 2: A coating is provided in this comparative example. The difference from Example 1 is that S2 is missing, and the photothermal material used in S3 is MXene without hydrophobic modification; the other components and their amounts are the same as those in Example 1.

[0048] Comparative Example 3: A coating is provided in this comparative example. The difference from Example 1 is that the amounts of epoxy resin, PDMS and their corresponding curing agents used in S3 are all doubled, and the other components and their amounts are the same as those in Example 1.

[0049] Experimental Example 1: Hydrophobic property test: The water contact angles of the MXene-based anti-icing superhydrophobic coatings prepared in each example and the comparative examples were measured using a water contact angle measuring instrument (MIC-100S, optical contact angle measuring instrument). The obtained results are shown in Table 1.

[0050] Table 1 Initial contact angles of the coatings in each example and comparative example

[0051] According to the data analysis in Table 1, it can be seen that: The contact angles of the MXene-based anti-icing superhydrophobic coatings prepared in Examples 1-5 all exceed 150°, showing excellent superhydrophobic properties ( Figure 1 is the intuitive comparison between Example 1 and the blank aluminum plate); Effect of modifier dosage: In Example 6, due to insufficient addition of long-chain silane, the contact angle was only 138°; in Example 7, although the silane dosage was increased, the improvement in hydrophobicity was limited, indicating the existence of modification saturation. Regulation of material ratio: In Example 8, due to too low addition of MXene (over-coated by resin / PDMS), the contact angle decreased to 121°; in Example 9, excessive addition of MXene did not significantly change the hydrophobicity, revealing the dispersion threshold of the material. Lack of key components in the system: In Comparative Example 2, unmodified MXene resulted in a contact angle of only 90°; in Comparative Example 3, due to excessive resin / PDMS inhibiting the action of hydrophobic groups, the contact angle remained at 120°.

[0052] Analysis of the results in Table 1 shows that: The grafting degree of silane on the surface of MXene and the material-binder ratio are crucial for the superhydrophobic performance of the coating; the MXene-based anti-icing superhydrophobic coating provided by the present invention has good superhydrophobic performance.

[0053] Experimental Example 2: Chemical stability test: The MXene-based anti-icing superhydrophobic coatings prepared in each Example and each Comparative Example were respectively immersed in strong acid (pH = 1), strong base (pH = 13) and sodium chloride solution, and the hydrophobicity of each coating was measured after 24 h.

[0054] Table 2 Contact angles of the coatings in each Example and Comparative Example after soaking in acid, base and salt for 24 h

[0055] It can be seen from the data analysis in Table 2 that: The MXene-based anti-icing superhydrophobic coatings prepared in Examples 1-5 could still maintain a contact angle of about 150° after 24 h in acid, base and salt solutions. After chemical immersion treatment, the contact angles of Examples 6 and 7 were maintained at 135 - 137° and 152 - 155° respectively. Due to insufficient addition of MXene in Example 8, after chemical immersion treatment, the contact angle remained at 118 - 121°. However, in Example 9, due to excessive MXene, after chemical immersion treatment, the un-fixed modified MXene structure in the coating was damaged by the acid-base solution, losing superhydrophobicity, and the contact angle dropped to 141 - 142°. The contact angle of Comparative Example 2 remained basically unchanged after chemical immersion treatment, while Comparative Example 3 had stronger tolerance to chemical immersion treatment due to excessive addition of resin, and the contact angle was maintained at 119 - 121°.

[0056] The above chemical stability test reflects that: The MXene-based anti-icing superhydrophobic coating described in the present application has excellent chemical stability.

[0057] Experimental Example 3: Mechanical Stability Test: The MXene-based anti-icing superhydrophobic coatings prepared in each example and each comparative example were subjected to 200 friction tests (each friction distance was 10 cm) in the horizontal direction under a load of 50 g weights.

[0058] Table 3 Contact Angles of Coatings in Each Example and Comparative Example after Sandpaper Friction

[0059] It can be obtained from the data analysis in Table 3 that: The MXene-based anti-icing superhydrophobic coatings prepared in Examples 1-5 can still maintain a contact angle of about 150° after experiencing sandpaper wear ( Figure 8 is the change in the surface water contact angle during the sandpaper friction process of Example 1); The hydrophobicity of Examples 6 and 7 decreased slightly after sandpaper friction, dropping to 132° and 151° respectively; Due to insufficient addition of MXene in Example 8, after experiencing sandpaper friction, the contact angle only decreased by 1° to 149°; while in Example 9, due to excessive MXene, most of the MXene in the coating was worn off after sandpaper friction, and the contact angle decreased significantly, losing superhydrophobicity; The contact angle of Comparative Example 2 decreased to 86° after sandpaper friction, while in Comparative Example 3, after sandpaper friction, the surface roughness increased, so the contact angle increased to 124°.

[0060] The above sandpaper friction test can reflect that: The MXene-based anti-icing superhydrophobic coating described in the present invention has excellent mechanical stability.

[0061] Experimental Example 4: Photothermal Performance Test: Photothermal heating experiments were carried out on the MXene-based anti-icing superhydrophobic coatings prepared in each example and each comparative example; specifically, a xenon lamp light source (PLS-SXE300+) was adjusted to 1 sun light intensity (100 mW / cm 2 ) using a light power meter (PL-MW 2000), and the coating was vertically irradiated for 360 s. An infrared thermal imager (HIKMICRO H21ProS+) was used to measure the temperature change on the surface of the coating during the illumination process. The distance between the xenon lamp and the coating was 20 cm, and the ambient temperature was room temperature (16°C).

[0062] Table 4 Maximum Temperatures of Photothermal Performance Tests of Coatings in Each Example and Comparative Example

[0063] It can be obtained from the data analysis in Table 4 that: After the MXene-based anti-icing superhydrophobic coatings prepared in Examples 1-7 and Comparative Examples 2 and 3 were irradiated with a xenon lamp at a simulated solar irradiance of 1 sun for 360 s, the temperature increased from 16 °C to 77.6-78.4 °C, while that of Comparative Example 1 only increased to 30.8 °C; In Example 8, due to insufficient addition of MXene, the maximum temperature after illumination remained at 75.5 °C. In Example 9, due to excessive addition of MXene, the maximum temperature after illumination could reach 81.5 °C, indicating that the addition amount of MXene is positively correlated with the photothermal performance of the coating, but excessive MXene does not result in a huge difference.

[0064] As Figure 2 shown, it is the heating curve of the photothermal performance test of Example 1, Example 8, Example 9 and Comparative Example 1; it can be seen from the figure that the MXene-based anti-icing superhydrophobic coating described in the present invention has good photothermal performance.

[0065] As Figure 3 shown, after 10 photothermal heating / cooling cycle tests, the coating prepared in Example 1 still has good photothermal performance.

[0066] The above shows that the MXene-based anti-icing superhydrophobic coating described in the present invention has excellent photothermal stability.

[0067] Experimental Example 5: Freezing and photothermal anti-icing performance test: The MXene-based anti-icing superhydrophobic coatings prepared in each example and each comparative example were tested for freezing and photothermal anti-icing using a refrigeration platform, a xenon light source and a power meter; specifically, the temperature of the refrigeration platform was set at -20 °C, the coating sample was placed on the refrigeration platform, 10 μL of deionized water was dropped on the surface of the coating, and the freezing process and time were recorded under the condition of no illumination. The freezing time was defined as the time from when the water droplet contacted the surface to when a small tip appeared at the top of the water droplet. Then the xenon light source was turned on, and the power meter was used to adjust the xenon light source to 1 sun irradiance (100 mW / cm 2 )), and the melting process and time were recorded. The anti-icing time was defined as the time from when the xenon light source irradiated the surface of the coating to when the ice completely melted into a liquid state.

[0068] Table 5 Freezing time and anti-icing time of the coatings in each example and comparative example

[0069] Table 5 The freezing and photothermal anti-icing performance tests show that: The icing and de-icing times of the MXene-based anti-icing superhydrophobic coatings prepared in Examples 1-5 were 523-553 s at -20 °C (only 16 s for the blank aluminum plate), and the de-icing time was 271-295 s under light illumination. The icing time was longer than the de-icing time, and the surface would not ice under light illumination ( Figure 4 and Figure 5 are the comparison diagrams of the beginning and end of icing and the beginning and end of de-icing for Example 1 and Comparative Example 1, respectively); For Example 6 (insufficient hydrophobic modification), the icing / de-icing times were 322 s / 310 s, respectively, and the performance was weakened; for Example 7 (excessive silane), the icing time was 544 s / de-icing 297 s, confirming that there is a modification threshold for hydrophobic modification; For Example 8 (insufficient MXene), the icing time dropped sharply to 100 s (de-icing 334 s), exposing the surface structure defects of the coating. For Example 9 (excessive MXene), the icing time was extended to 584 s (de-icing 237 s), and the contact area between the coating and water droplets was small; For Comparative Example 2 (unmodified), the icing time was 27 s / de-icing 303 s, and for Comparative Example 3 (excessive resin), the icing time was 39 s / de-icing 270 s, proving that the lack of the MXene-hydrophobic synergistic system could not achieve effective anti-icing and de-icing.

[0070] The above icing and photothermal de-icing performance tests can reflect that the MXene-based anti-icing superhydrophobic coating described in the present invention has excellent passive anti-icing and photothermal active de-icing performances.

[0071] Experimental Example 6: Photothermal de-icing layer and defrosting test: The MXene-based anti-icing superhydrophobic coatings prepared in each example and each comparative example were subjected to photothermal de-icing layer and defrosting tests using a refrigeration platform, a xenon light source, and a light power meter; specifically, the temperature of the refrigeration platform was set to -20 °C, the coating sample was placed on the refrigeration platform, an ice layer / natural frost layer with a thickness of 2 mm was placed above the coating, and then the xenon light source was turned on, and the xenon light source was adjusted to 1 sun illumination intensity (100 mW / cm 2 ) using the light power meter, and the melting process and time of the ice layer / frost layer were recorded.

[0072] Table 6 Icing time and de-icing time of the coatings in each example and comparative example

[0073] It can be obtained from the data analysis in Table 6 that: The de-icing layer times of the MXene-based anti-icing superhydrophobic coatings prepared in Examples 1-5 were between 536-559 s, and the defrosting times were between 88-98 s ( Figure 6 and Figure 7 are the comparison diagrams of the beginning and end of icing and the beginning and end of de-icing for Example 1 and Comparative Example 1, respectively); Although the silane content was changed in Example 6 and Example 7, it had basically no effect on the photothermal performance of MXene. Therefore, the difference in the ice removal and defrosting times compared to Example 1 was small. In Example 8, due to insufficient addition of MXene, the ice layer removal time was significantly extended to 1549 s, and the defrosting time was also extended to 114 s. In Example 9, although an excessive amount of MXene was added, the ice layer removal time and defrosting time only decreased slightly, to 510 s and 86 s respectively. Comparative Example 1 was a blank aluminum plate, which could not remove ice and frost autonomously under light illumination. In Comparative Example 2, MXene was not hydrophobically modified, resulting in better contact between the water after ice and frost melting and the coating, and the icing time and frosting time were extended to 987 s and 187 s respectively. In Comparative Example 3, due to the addition of an excessive amount of resin, the water after ice layer melting remained on the surface, and the icing time was extended to 1335 s, and the frosting time was only extended to 100 s.

[0074] The above test results of photothermal ice layer removal and defrosting show that the MXene-based ice removal superhydrophobic coating of the present invention has excellent photothermal ice removal and defrosting performance.

[0075] Experimental Example 7: Cable ice removal test: The substrate in Example 1 was replaced with a 2×1.5 mm2 cable, and the MXene-based ice removal superhydrophobic coating of the present invention was sprayed on the surface of the cable, with a blank cable for comparison.

[0076] A photothermal ice removal test was carried out on the coated cable and the blank cable using a refrigeration platform, a xenon light source, and a light power meter; specifically, the cable was placed in a centrifuge tube filled with water, frozen in a refrigerator, taken out and placed on the refrigeration platform, the temperature of the refrigeration platform was set to -20 °C, then the xenon light source was turned on, and the xenon light source was adjusted to 1 sun illumination intensity (100 mW / cm 2 ) using the light power meter, and the ice melting process on the cable surface within 10 min was recorded.

[0077] As Figure 9 shown, before illumination, there were ice layers on the surfaces of both the coated cable and the blank cable; after 10 min of illumination, only a corner of the ice layer on the blank cable melted, while the ice layer on the surface of the coated cable was basically completely melted, and the supercooled water on the surface basically all slipped off, indicating good photothermal ice removal performance of the cable surface.

[0078] The above cable ice removal test results show that the MXene-based ice removal superhydrophobic coating of the present invention has good practical application effects and prospects.

[0079] Obviously, the above are the preferred embodiments of the present application, but they should not be construed as limiting the scope of the present application. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present application, several improvements and refinements can be made, and these improvements and refinements are also regarded as the protection scope of the present application.

Claims

1. A deicing super-hydrophobic coating based on MXene, characterized in that: The invention comprises the following components in percentage by weight: 2% to 5% of superhydrophobic modified MXene photothermal material, 2% to 5% of epoxy resin, 0.5% to 1.5% of epoxy resin curing agent, 0.5% to 1.5% of PDMS, 0.05% to 0.15% of PDMS curing agent, and 80% to 90% of diluent; Wherein, the super-hydrophobic modified MXene photothermal material is MXene powder treated with fluorine-free long-chain silane; The epoxy resin is one of epoxy resin E-44, E-51, E-20, and E-42; The epoxy resin curing agent is one of 593 curing agent, polyetheramine 230 curing agent and T-31 curing agent; The PDMS and the PDMS curing agent are Dow Corning DC184 main agent and corresponding curing agent; The diluent is one or more of ethyl acetate, butyl acetate, toluene, acetone and n-hexane.

2. A MXene-based deicing super-hydrophobic coating according to claim 1, characterized in that: The fluorine-free long-chain silane includes hexadecyltrimethoxysilane, octadecyltrimethoxysilane or dodecyltrimethoxysilane.

3. A method for preparing a deicing super-hydrophobic coating based on MXene, characterized in that: The steps include: S1 Preparation of MXene After mixing concentrated HCl and water into a hydrochloric acid solution, add LiF into the hydrochloric acid solution and stir to mix. Then slowly add Ti3AlC2 into the above mixture. Seal the container and place it in a water bath at 35-45℃ and stir for 18-36 hours. The reaction mixture was centrifuged and washed with ultrapure water until the pH of the supernatant was ≥ 6, the precipitate was collected and dispersed in ultrapure water, and then ultrasonicated for 1 to 2 hours under ice water bath conditions to obtain a MXene suspension. The suspension is centrifuged to obtain MXene colloid, and vacuum freeze-dried for 24 to 48 hours to obtain MXene powder; S2 Preparation of superhydrophobic modified MXene photothermal materials The MXene powder prepared by S1 was added to an ethanol solution containing fluorine-free long-chain silane, stirred and reacted at room temperature for 12 to 24 hours, centrifuged, the supernatant was removed, and vacuum freeze-dried for 24 to 48 hours to obtain a superhydrophobic modified MXene photothermal material; S3 Preparation of MXene-based deicing superhydrophobic coating The diluent is divided into two equal parts, and the super-hydrophobic modified MXene photothermal material prepared in S2 is added to one of the diluents, and stirred until uniformly dispersed; the epoxy resin and PDMS are added to the other diluent, and stirred until uniformly dispersed; after the two diluents are mixed, the epoxy resin curing agent and the PDMS curing agent are added, and stirred again to obtain a deicing super-hydrophobic coating based on MXene; Among them, the mass percentage of each component is: superhydrophobic modified MXene photothermal material 2% to 5%, epoxy resin 2% to 5%, epoxy resin curing agent 0.5% to 1.5%, PDMS 0.5% to 1.5%, PDMS curing agent 0.05% to 0.15%, and diluent 80% to 90%.

4. A method for preparing a deicing super-hydrophobic coating based on MXene according to claim 3, characterized in that: In S1, the concentration of the hydrochloric acid solution is 9 mol / L, and the mass ratio of LiF to Ti3AlC2 is (1-1.6):

1.

5. A method for preparing a deicing super-hydrophobic coating based on MXene according to claim 3, characterized in that, In S2, the mass ratio of the MXene powder, the long-chain silane and the diluent is (1-2):(1-2):

50.

6. A method for preparing a deicing super-hydrophobic coating based on MXene according to claim 3, characterized in that: The epoxy resin is one of epoxy resin E-44, E-51, E-20, and E-42; The epoxy resin curing agent is one of 593 curing agent, polyetheramine 230 curing agent and T-31 curing agent; The PDMS and the PDMS curing agent are Dow Corning DC184 main agent and corresponding curing agent; The diluent is one or more of ethyl acetate, butyl acetate, toluene, acetone, and n-hexane. The fluorine-free long-chain silane includes hexadecyltrimethoxysilane, octadecyltrimethoxysilane or dodecyltrimethoxysilane.

7. A MXene-based deicing superhydrophobic coating, characterized in that: It is prepared using the MXene-based deicing super-hydrophobic coating as described in claim 1 or 2.

8. A method for preparing a deicing super-hydrophobic coating based on MXene, characterized in that: The super hydrophobic coating prepared according to any one of claims 3 to 7 is sprayed on a substrate by a spraying method, and after constant temperature curing, a MXene-based deicing super hydrophobic coating with passive anti-icing and active photothermal deicing is obtained.

9. The method for preparing a deicing super-hydrophobic coating based on MXene according to claim 8, characterized in that: The substrate was pretreated before spraying: the substrate was polished with sandpaper and then ultrasonically cleaned with ethanol and ultrapure water; during spraying, the spray pressure of the spray gun was 2 bar to 4 bar, the nozzle diameter of the spray gun was 0.3 to 0.8 mm, and the distance between the nozzle and the substrate was 15 to 20 cm.

10. An application of a deicing super-hydrophobic coating based on MXene, characterized in that: The MXene-based deicing superhydrophobic coating as described in claim 7 or the MXene-based deicing superhydrophobic coating prepared as claimed in claim 8 or 9 is applied to the aerospace field, wind power generation, wires and cables or other power facilities.

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