Preparation method of multifunctional super-hydrophobic coating with excellent durable anti-corrosion and anti-icing performance

Abstract

The application discloses a kind of multifunctional super-hydrophobic coating preparation method with excellent durable anticorrosion and anti-icing performance, it is related to the technical field of hydrophobic coating preparation, including the following steps: FEVE and curing agent thereof and EP and curing agent thereof are respectively dissolved in butyl acetate, ultrasonic oscillation and mechanical stirring obtain solution A and solution B;SiO2 Powder and FDTs are dispersed in butyl acetate, and stirring obtains modified SiO2 solution;Carbon black, solution A and solution B are sequentially added to the modified solution, ultrasonic dispersion, mechanical stirring, the mixed solution is sprayed, and then solidified in drying oven.The super-hydrophobic coating of the method of the present application can be prepared on aluminum sheet, paperboard, white paper and wood board and the like substrates, and all exhibit excellent stain resistance and self-cleaning properties;Super-hydrophobic coating exhibits good mechanical stability, adhesion, physical / chemical stability, corrosion resistance, anti-icing, deicing and the like performance;The preparation method of super-hydrophobic coating is simple, low in cost, can be prepared on a large scale, and can be widely applied.

Description

Technical Field

[0001] This invention relates to the technical field of hydrophobic coating preparation, specifically to a method for preparing a multifunctional superhydrophobic coating with excellent durability, corrosion resistance, and anti-icing properties. Background Technology

[0002] Protective coatings formed by organic coatings are a simple, effective, and economical strategy for addressing material wear and corrosion problems across various industries. Commonly used organic coatings include polyurethane, acrylic, silicone, epoxy, and fluorocarbon resins. Among these, fluorocarbon resin (FEVE) coatings are widely used in the field of protective coatings due to their superior weather resistance, corrosion resistance, good adhesion to substrates, and strong chemical resistance. However, FEVE coatings are brittle and prone to cracking or peeling under harsh working conditions, often leading to wear and corrosion, thus severely reducing their durability. Furthermore, the low surface activity of the CF bonds in FEVE results in weak intermolecular forces in fluorinated compounds and poor compatibility with other materials, which also limits the widespread application of FEVE in the coatings field. Currently, research on the modification of FEVE coatings to enhance their durability and corrosion resistance has attracted considerable attention. Summary of the Invention

[0003] The purpose of this invention is to provide a method for preparing a multifunctional superhydrophobic coating with excellent durability, corrosion resistance, and anti-icing properties, so as to overcome the above-mentioned defects in the prior art.

[0004] A method for preparing a multifunctional superhydrophobic coating with excellent durability, corrosion resistance, and anti-icing properties includes the following steps:

[0005] S1. Fluorocarbon resin and its curing agent are dissolved in butyl acetate at a mass ratio of 10:1 and epoxy resin and its curing agent at a mass ratio of 3:1, respectively. The solutions A and B are obtained by ultrasonic vibration and mechanical stirring.

[0006] S2. SiO2 powder and 1H,1H,2H,2H-perfluorodecyltrimethoxysilane are dispersed in butyl acetate and then mechanically stirred at room temperature to obtain a modified SiO2 solution.

[0007] S3. Add carbon black, solution A and solution B to the modified solution in sequence, disperse by ultrasonication, then stir mechanically, spray the final mixed solution, and then cure it in a drying oven.

[0008] Preferably, in step S1, 1.5-5.0g of fluorocarbon resin and 0.15-0.5g of its curing agent are dissolved in 8g of butyl acetate at a mass ratio of 10:1, and 1.5-5g of epoxy resin and 0.5-1.67g of its curing agent are dissolved in 8g of butyl acetate at a mass ratio of 3:1.

[0009] Preferably, in step S1, ultrasonic oscillation for 10 minutes and mechanical stirring for 10 minutes are used to obtain uniformly dispersed solutions A and B.

[0010] Preferably, in step S2, 1g of SiO2 powder and 0.08g of 1H,1H,2H,2H-perfluorodecyltrimethoxysilane are dispersed in 15g of butyl acetate.

[0011] Preferably, in step S2, the modified SiO2 solution is mechanically stirred at 500 r / min for 1 h at room temperature to obtain a uniformly dispersed solution.

[0012] Preferably, in step S3, 0.2g of carbon black, solution A, and solution B are added sequentially to the modified solution.

[0013] Preferably, in step S3, the mixture is ultrasonically dispersed for 20 min, then mechanically stirred for 30 min, and the final mixture is sprayed at a pressure of 0.5 MPa at a distance of 20 cm above the aluminum plate for 30 s, and then cured in a drying oven at 60°C for 5 h.

[0014] The present invention has the following advantages:

[0015] (1) The superhydrophobic coating of the method of this application can be prepared on substrates such as aluminum sheet, cardboard, white paper and wood board, and all exhibit excellent antifouling and self-cleaning properties;

[0016] (2) The superhydrophobic coating of the method of this application exhibits good mechanical stability, adhesion, physical / chemical stability, corrosion resistance, anti-icing and de-icing properties;

[0017] (3) The method of this application for preparing superhydrophobic coating is simple, low cost, and can be prepared on a large scale. It is expected to be widely used in construction, transportation, chemical industry and other fields. Attached Figure Description

[0018] Figure 1 Microscopic morphology of the coating surface: (ae) distribution of the main elements C, O, F and Si on the coating surface and (fi) SEM image of the coating surface.

[0019] Figure 2 (a) FTIR of the coating; XPS spectrum of the coating; (b) C1s; (c) F1s; (d) total surface spectrum.

[0020] Figure 3Self-cleaning behavior and silver mirror phenomenon of superhydrophobic coating on different substrate surfaces: (a) paper; (b) tinplate; (c) aluminum plate; (d) carbon steel; (e) lead block; (f) silver mirror phenomenon; Self-cleaning and anti-fouling behavior of superhydrophobic coating on different liquids and fine sand: (g) water; (h) mud; (i) milk; (j) orange juice; (k) coffee; (l) pigment water; (mo) fine sand.

[0021] Figure 4 (a) Schematic diagram of the abrasion test; (b) Wetting properties of the coating under different abrasion cycles; (cd) SEM image after 400 abrasion cycles.

[0022] Figure 5 This is an adhesion test diagram of the CB / SiO2-FEVE / EP coating.

[0023] Figure 6 The figures show the durability test results of the coating in (a) solutions with different pH values, (b) 3.5 wt.% NaCl solution, and (c) under ultraviolet irradiation.

[0024] Figure 7 The diagram shows the process of water droplet freezing on (a) the aluminum plate and (b) the superhydrophobic coating surface; and the anti-icing mechanism on (c) the aluminum plate and (d) the superhydrophobic coating surface.

[0025] Figure 8 The figures show (a) the temperature change of the CB / SiO2-FEVE / EP coating surface under simulated sunlight irradiation over time; (b) the highest temperature of the aluminum plate and (c) the superhydrophobic coating surface under simulated sunlight irradiation; and (d) the melting process of ice on the aluminum plate and (e) the superhydrophobic coating surface under simulated sunlight irradiation.

[0026] Figure 9 Tafel curves for EP and FEVE samples with different ratios.

[0027] Figure 10 EIS curves (ab) and Nyquist curves (c) for samples with different ratios of EP and FEVE; (d) Phase plot. Detailed Implementation

[0028] The following detailed description of the embodiments, with reference to the accompanying drawings, will further illustrate the specific implementation of the present invention, in order to help those skilled in the art to have a more complete, accurate, and in-depth understanding of the concept and technical solutions of the present invention.

[0029] Example 1:

[0030] FEVE (5g) and its curing agent (0.5g) were dissolved in 16g of butyl acetate at a mass ratio of 10:1 (where FEVE:EP=5:0), and mechanically stirred for 10 min to obtain a uniformly dispersed solution A.

[0031] 1 g of SiO2 powder and 0.08 g of FDTs were dispersed in 15 g of butyl acetate, and then mechanically stirred at 500 r / min for 1 h at room temperature to obtain a uniformly dispersed modified SiO2 solution. 0.2 g of CB and solution A were then added sequentially to the modified solution, ultrasonically dispersed for 20 min, and then mechanically stirred for 30 min. The final mixture was sprayed at a pressure of 0.5 MPa at a distance of 20 cm above a pretreated aluminum plate for 30 s, and then cured in a 60 ℃ oven for 5 h.

[0032] Example 2:

[0033] FEVE (3.5 g) and its curing agent (0.35 g) were dissolved in 8 g of butyl acetate at a mass ratio of 10:1 and EP (1.5 g) and its curing agent (0.5 g) at a mass ratio of 3:1 (where FEVE:EP = 3.5:1.5). The mixture was mechanically stirred for 10 min to obtain uniformly dispersed solutions A and B.

[0034] 1 g of SiO2 powder and 0.08 g of FDTs were dispersed in 15 g of butyl acetate, and then mechanically stirred at 500 r / min for 1 h at room temperature to obtain a uniformly dispersed modified SiO2 solution. 0.2 g of CB, solution A, and solution B were then added sequentially to the modified solution, ultrasonically dispersed for 20 min, and then mechanically stirred for 30 min. The final mixture was sprayed at a pressure of 0.5 MPa at a distance of 20 cm above a pretreated aluminum plate for 30 s, and then cured in a 60 ℃ oven for 5 h.

[0035] Example 3:

[0036] FEVE (2.5 g) and its curing agent (0.25 g) were dissolved in 8 g of butyl acetate at a mass ratio of 10:1 and EP (2.5 g) and its curing agent (0.83 g) at a mass ratio of 3:1 (where FEVE:EP = 1:1). The mixture was mechanically stirred for 10 min to obtain uniformly dispersed solutions A and B.

[0037] 1 g of SiO2 powder and 0.08 g of FDTs were dispersed in 15 g of butyl acetate, and then mechanically stirred at 500 r / min for 1 h at room temperature to obtain a uniformly dispersed modified SiO2 solution. 0.2 g of CB, solution A, and solution B were then added sequentially to the modified solution, ultrasonically dispersed for 20 min, and then mechanically stirred for 30 min. The final mixture was sprayed at a pressure of 0.5 MPa at a distance of 20 cm above a pretreated aluminum plate for 30 s, and then cured in a 60 ℃ oven for 5 h.

[0038] Example 4:

[0039] FEVE (1.5 g) and its curing agent (0.15 g) were dissolved in 8 g of butyl acetate at a mass ratio of 10:1 and EP (3.5 g) and its curing agent (1.17 g) at a mass ratio of 3:1 (where FEVE:EP = 1.5:3.5). The mixture was mechanically stirred for 10 min to obtain uniformly dispersed solutions A and B.

[0040] 1 g of SiO2 powder and 0.08 g of FDTs were dispersed in 15 g of butyl acetate, and then mechanically stirred at 500 r / min for 1 h at room temperature to obtain a uniformly dispersed modified SiO2 solution. 0.2 g of CB, solution A, and solution B were then added sequentially to the modified solution, ultrasonically dispersed for 20 min, and then mechanically stirred for 30 min. The final mixture was sprayed at a pressure of 0.5 MPa at a distance of 20 cm above a pretreated aluminum plate for 30 s, and then cured in a 60 ℃ oven for 5 h.

[0041] Example 5:

[0042] EP (5 g) and its curing agent (1.67 g) were dissolved in 16 g of butyl acetate at a mass ratio of 3:1 (where FEVE:EP=0:5), and mechanically stirred for 10 min to obtain a uniformly dispersed solution B.

[0043] 1 g of SiO2 powder and 0.08 g of FDTs were dispersed in 15 g of butyl acetate, and then mechanically stirred at 500 r / min for 1 h at room temperature to obtain a uniformly dispersed modified SiO2 solution. 0.2 g of CB, solution A, and solution B were then added sequentially to the modified solution, ultrasonically dispersed for 20 min, and then mechanically stirred for 30 min. The final mixture was sprayed at a pressure of 0.5 MPa at a distance of 20 cm above a pretreated aluminum plate for 30 s, and then cured in a 60 ℃ oven for 5 h.

[0044] in, Figure 1The microstructure of the coating surface in Example 3 is shown below: (ae) Distribution of the main elements C, O, F, and Si on the coating surface; (fi) SEM images of the coating surface at different magnifications. The coating surface exhibits obvious protrusions, depressions, and pores. The pores can trap air to form a stable air layer, effectively utilizing the permeation pathway. Furthermore, there is no obvious gap between the organic and inorganic phases, indicating good compatibility between the modified nanoparticles and the organic coating with CF bonds. This is beneficial for achieving superhydrophobicity in the coating, ensuring low contact area and deep penetration of droplets on the coating.

[0045] in addition, Figure 2 (a) FTIR of the coating; XPS spectrum of the coating; (b) C1s; (c) F1s; (d) Overall surface spectrum. The chemical composition of the coating surface was investigated in detail using FTIR and XPS. The CF bonds of FEVE and the groups in EP were successfully combined in the FTIR spectrum to enhance coating performance. The XPS spectrum of the coating surface was further used to precisely elucidate the chemical groups in the composite filler. This confirmed the presence of FEVE and EP in the coating and their synergistic effect in enhancing coating adhesion and corrosion resistance.

[0046] also, Figure 3 The self-cleaning behavior and silver mirror phenomenon of the superhydrophobic coating on different substrate surfaces: (a) paper; (b) tinplate; (c) aluminum plate; (d) carbon steel; (e) lead block; (f) silver mirror phenomenon; Self-cleaning and antifouling behavior of the superhydrophobic coating on different liquids and fine sand: (g) water; (h) mud; (i) milk; (j) orange juice; (k) coffee; (l) pigment water; (mo) fine sand. Water droplets quickly slide off without leaving any residue on the coating surface; the silver mirror phenomenon indicates that the coating is superhydrophobic; the above phenomena demonstrate a significant antifouling effect.

[0047] in addition, Figure 4 The abrasion test was conducted using sandpaper. (a) Schematic diagram of the abrasion test; (b) Wettability of the coating under different abrasion cycles; (cd) SEM image after 400 abrasion cycles. After 200 abrasion cycles, the CA change was negligible, while SA increased from 3° to 7.5°, indicating that the coating effectively maintained its adhesion to the substrate during multiple abrasion cycles. After 400 abrasion cycles, the CA of the coating surface slowly decreased, while SA gradually increased, indicating that the micro-nano structure of the coating surface was damaged under the action of abrasion, and some of the surface nanoparticles were lost due to the mechanical movement of friction. Even so, the overall structure still exists and does not affect the hydrophobicity of the coating. However, it is clearly visible in the figure that as the damage to the coating intensifies with abrasion, the loss of hydrophobic properties of the coating is inevitable. Figure 5Although SA is 10°, CA still meets the requirement (>150°), indicating that the coating has durable mechanical abrasion resistance and excellent adhesion, enabling it to withstand the challenges of repeated sandpaper abrasion.

[0048] also, Figure 5 The adhesion test results for the CB / SiO2-FEVE / EP coating in the above example are shown. The results demonstrate excellent coating adhesion while maintaining hydrophobicity. This demonstrates that coatings providing a physical barrier to the material surface offer significant advantages in improving coating durability and can substantially extend the coating's service life, highlighting its practical applicability across various industries.

[0049] in, Figure 6 Durability tests of the coating were conducted in (a) solutions with different pH values, (b) a 3.5 wt.% NaCl solution, and (c) under ultraviolet irradiation. It can be noted that the WCA (water content of the coating) on ​​the surface of the CB / SiO2-FEVE / EP coating did not change significantly with different pH solutions and salt solutions, showing only slight increases or decreases, indicating excellent hydrophobicity and resistance to acids, alkalis, and salts. Figure 6 (c) shows the changes in the wetting state of the coating after UV irradiation at different times. The results indicate that under continuous strong UV irradiation for 7 days, the WCA of the coating remains at around 161°, demonstrating excellent outdoor practicality. In summary, the prepared coating exhibits strong resistance to various harsh conditions, including strong UV irradiation, acidic, alkaline, and saline solution environments.

[0050] It is important to note that Figure 7 The process of water droplet icing on (a) the aluminum plate and (b) the superhydrophobic coating surface; and (c) the anti-icing mechanism on the aluminum plate and (d) the superhydrophobic coating surface. Among these, in... Figure 7 In (a), the time it takes for a water droplet to freeze from the moment it falls on the aluminum plate is 198 seconds. Figure 7 The icing time recorded on the coating in (b) is 570 s. The phenomena shown in the figure indicate that the coating exhibits better anti-icing performance compared to the aluminum plate, and the time is extended by approximately 2.88 times.

[0051] besides, Figure 8Figure 8(de) shows the temperature change of the CB / SiO2-FEVE / EP coating surface over time under simulated sunlight irradiation; (b) the highest temperature of the aluminum plate and (c) the superhydrophobic coating surface under simulated sunlight irradiation; and (d) the melting process of ice on the aluminum plate and (e) the superhydrophobic coating surface under simulated sunlight irradiation. At room temperature, the initial temperature measured by the thermal infrared camera was 25.2℃. After a period of simulated sunlight irradiation, the highest temperature of the aluminum plate surface stabilized at 29.6℃ after 120s, while the highest temperature of the sample surface stabilized at 70.9℃ after 600s. The 41.3℃ temperature difference between the sample surface and the aluminum plate surface is attributed to the high photothermal conversion efficiency of CB. Figure 8(de) shows that under sunlight irradiation, the coating surface rapidly heats up due to the photothermal effect of CB, causing the ice on the coating surface to melt quickly. The superhydrophobic properties then cause the melted water to roll away from the coating surface, leaving a clean surface and achieving a self-de-icing effect.

[0052] in, Figure 9 Tafel curves for EP and FEVE samples. Based on the corrosion inhibition efficiency calculation formula. The corrosion inhibition efficiency is approximately 99.87%, which is attributed to the superior shielding properties of FEVE and EP, resulting in better corrosion protection. The coating prepared at this stage reduces the corrosion current density by approximately three orders of magnitude compared to the aluminum plate surface. Research data confirms the coating's superior corrosion protection performance.

[0053] in addition, Figure 10 EIS curves (ab) and Nyquist curves (c) for EP and FEVE examples; (d) Bode plot; (e) Phase plot. The data shows that the appropriate allocation of different polymer addition amounts is crucial for improving coating performance. It can not only effectively mitigate microporous defects inherent in the coating itself and enhance its shielding ability against corrosive media, thus effectively improving the coating's corrosion resistance, but also provide a physical barrier for the metal, effectively enhancing the coating's corrosion resistance.

[0054] The present invention has been described above by way of example with reference to the accompanying drawings. Obviously, the specific implementation of the present invention is not limited to the above-described manner. Any non-substantial improvements made using the concept and technical solution of the present invention, or the direct application of the present invention and technical solution to other situations without modification, are all within the protection scope of the present invention.

Claims

1. A method for preparing a multifunctional superhydrophobic coating with excellent durability, corrosion resistance, and anti-icing properties, characterized in that: Includes the following steps: S1. Fluorocarbon resin and its curing agent are dissolved in butyl acetate at a mass ratio of 10:1 and epoxy resin and its curing agent at a mass ratio of 3:1, respectively. The solutions A and B are obtained by ultrasonic vibration and mechanical stirring. S2. SiO2 powder and 1H,1H,2H,2H-perfluorodecyltrimethoxysilane are dispersed in butyl acetate and then mechanically stirred at room temperature to obtain a modified SiO2 solution. S3. Add carbon black, solution A and solution B to the modified solution in sequence, disperse by ultrasonication, then stir mechanically, spray the final mixed solution, and then cure it in a drying oven; In step S1, 1.5-5.0g of fluorocarbon resin and 0.15-0.5g of its curing agent are dissolved in 8g of butyl acetate at a mass ratio of 10:1, and 1.5-5g of epoxy resin and 0.5-1.67g of its curing agent are dissolved in 3:

1. In step S1, ultrasonic oscillation for 10 minutes and mechanical stirring for 10 minutes are used to obtain uniformly dispersed solutions A and B. In step S2, 1g of SiO2 powder and 0.08g of 1H,1H,2H,2H-perfluorodecyltrimethoxysilane are dispersed in 15g of butyl acetate.

2. The method for preparing a multifunctional superhydrophobic coating with excellent durability, corrosion resistance, and anti-icing properties according to claim 1, characterized in that: In step S2, the modified SiO2 solution is mechanically stirred at 500 r / min for 1 h at room temperature to obtain a uniformly dispersed solution.

3. The method for preparing a multifunctional superhydrophobic coating with excellent durability, corrosion resistance, and anti-icing properties according to claim 1, characterized in that: In step S3, 0.2g of carbon black, solution A, and solution B are added sequentially to the modified solution.

4. The method for preparing a multifunctional superhydrophobic coating with excellent durability, corrosion resistance, and anti-icing properties according to claim 1, characterized in that: In step S3, ultrasonic dispersion is performed for 20 min, followed by mechanical stirring for 30 min. The final mixture is then sprayed at a pressure of 0.5 MPa at a distance of 20 cm above the aluminum plate for 30 s, and then cured in a 60°C drying oven for 5 h.

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