A dual-size wear-resistant super-hydrophobic material based on a phase separation method, a preparation method and applications thereof

Abstract

The application relates to the field of inorganic materials, in particular to a double-size wear-resistant super-hydrophobic material based on a phase separation method, which comprises double-size semi-solid PF-SiO2 nanoparticles containing ethanol, polyolefin glue water and butyl acetate, wherein the double-size semi-solid PF-SiO2 nanoparticles containing ethanol comprise large-size semi-solid PF-SiO2 nanoparticles and small-size semi-solid PF-SiO2 nanoparticles, and the preparation method comprises the following steps: uniformly mixing SiO2 nanoparticles with an ethanol solution, uniformly stirring after adding sodium methyl silicate, mechanically stirring and reacting after adding PFDTES and tetraethyl orthosilicate, forming a suspension, centrifuging the suspension to obtain semi-solid PF-SiO2 nanoparticles containing ethanol, dissolving polyolefin glue water (POA) in butyl acetate, stirring for 20-25 min, and adding the large-size semi-solid PF-SiO2 nanoparticles and the small-size semi-solid PF-SiO2 nanoparticles under stirring, and stirring for 3-3.5 h to obtain a POA / modified SiO2 suspension. Through the implementation of the scheme, a super-hydrophobic material with good hydrophobic performance and high wear resistance can be obtained.

Description

Technical Field

[0001] This invention relates to the field of inorganic materials, specifically to a dual-size wear-resistant superhydrophobic material based on phase separation, its preparation method, and its application. Background Technology

[0002] Good mechanical stability is a prerequisite for the practical application of superhydrophobic surfaces. However, most superhydrophobic surfaces inherently possess poor mechanical stability because wear easily disrupts their layered structure due to mechanical stress concentration. This is a major obstacle limiting their practical application. To address this issue, researchers have made significant progress in improving mechanical stability through methods such as using composite wear-resistant materials (CN118027782A), designing self-healing surfaces (CN112724782B), constructing self-similar structures (CN119500522A), and building protective microstructures (CN113604095B). Furthermore, in terms of preparation methods, methods such as laser etching, template methods, and electrochemical methods are limited by equipment constraints, restricting the large-scale preparation of superhydrophobic coatings. Spraying and dip coating methods, on the other hand, are not subject to these limitations and can expand the application of superhydrophobic coatings to more fields.

[0003] CN 108864778 A discloses a micron-nano hierarchical superhydrophobic coating composed of dual-size SiO2 particles and its preparation method. The method involves mixing two different sizes of SiO2 particles with ethanol, then adding organosilane and ultrasonically dispersing them uniformly to obtain the superhydrophobic coating. Although the coating improves hydrophobicity, it utilizes the weak interaction force between particles and the Ostwald ripening mechanism to achieve a stable and tight bond between the large and small SiO2 particles. Therefore, the wear resistance of the coating is not high, and it cannot be used in scenarios with high wear resistance requirements.

[0004] Therefore, it is necessary to develop a superhydrophobic material with good hydrophobic properties and high wear resistance. Summary of the Invention

[0005] One of the objectives of this invention is to provide a dual-size wear-resistant superhydrophobic material based on phase separation, which, through the synergistic combination and precise proportion of each component, can improve both the wear resistance and hydrophobicity of the coating.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: a dual-size wear-resistant superhydrophobic material based on phase separation method, comprising dual-size ethanol-containing semi-solid PF-SiO2 nanoparticles, polyolefin adhesive and butyl acetate, wherein the dual-size ethanol-containing semi-solid PF-SiO2 nanoparticles include large-size semi-solid PF-SiO2 nanoparticles and small-size semi-solid PF-SiO2 nanoparticles.

[0007] Preferably, as an improvement, the ratio of the dual-size ethanol-containing semi-solid PF-SiO2 nanoparticles to the polyolefin adhesive is 2.4 to 5.0.

[0008] Preferably, as an improvement, the ratio of large-size semi-solid PF-SiO2 nanoparticles to small-size semi-solid PF-SiO2 nanoparticles is 5:(2-5).

[0009] Preferably, as an improvement, the particle size of the large-size semi-solid PF-SiO2 nanoparticles is 100-200 nm.

[0010] Preferably, as an improvement, the particle size of the small-sized semi-solid PF-SiO2 nanoparticles is 10-20 nm.

[0011] The second objective of this invention is to provide a method for preparing a dual-size wear-resistant superhydrophobic material based on phase separation. By implementing this method, PF-SiO2 nanoparticles are tightly wrapped around the surface of POA microspheres, forming a dense but rough surface at the nanoscale, and generating micron and nano-scale self-similar structures on the surface, thereby significantly improving the hydrophobicity and wear resistance of the superhydrophobic coating.

[0012] A method for preparing a dual-size wear-resistant superhydrophobic material based on phase separation includes the following steps:

[0013] S1. Synthesis of dual-size ethanol-containing semi-solid PF-SiO2 nanoparticles: Two types of SiO2 nanoparticles with different particle sizes were synthesized separately. The synthesis steps were as follows: SiO2 nanoparticles were mixed with ethanol solution, sodium methylsilicate was added and stirred evenly, 1H,1H,2H,2H-perfluorodecyltriethoxysilane (PFDTES) and tetraethyl orthosilicate were added and mechanically stirred to form a suspension. The suspension was centrifuged to obtain ethanol-containing semi-solid PF-SiO2 nanoparticles.

[0014] S2. Dissolve polyolefin adhesive (POA) in butyl acetate and stir for 20-25 min. Then, while stirring, add large-sized semi-solid PF-SiO2 nanoparticles and small-sized semi-solid PF-SiO2 nanoparticles and stir for 3-3.5 h to obtain a POA / modified SiO2 suspension.

[0015] Preferably, as an improvement, in step S1, the addition ratio of SiO2 nanoparticles to ethanol solution is 1g:(65-75)ml; the ethanol solution comprises 23 parts ethanol and 2 parts water.

[0016] Preferably, as an improvement, in step S1, the mass ratio of SiO2 nanoparticles: sodium methylsilicate: PFDTES: tetraethyl orthosilicate is 1:0.3:(1.63~1.67):0.28. The mass ratio mentioned here refers to the effective mass added. For example, if 1g of sodium methylsilicate is added, but the solid content of sodium methylsilicate is 30%, then a mass ratio of 0.3 is used.

[0017] Preferably, as an improvement, in step S1, the SiO2 nanoparticles are mixed with the ethanol solution by sequentially mechanical stirring for 15 min and ultrasonic treatment for 15 min.

[0018] A dual-size wear-resistant superhydrophobic material based on phase separation method is applied to the coating field. When using it, the dual-size wear-resistant superhydrophobic material is sprayed onto the substrate with a spray gun and cured at room temperature for 24 hours to obtain a phase-separated superhydrophobic coating.

[0019] The principle and advantages of this scheme are:

[0020] 1. To improve the wear resistance of the coating, this solution proposes a completely opposite approach to traditional methods. The traditional method involves applying a modification layer to the SiO2 surface to delay the wear time of the SiO2. During the wear process, the modification layer is worn away first, followed by the underlying SiO2. As the SiO2 is gradually worn away, the superhydrophobicity is gradually lost. While this method can extend the friction cycle of the coating to some extent, its inherent wear resistance is poor. This solution, however, takes the opposite approach. Through a special preparation process, PF-SiO2 is encapsulated on the POA surface. Because PF-SiO2 is inherently wear-resistant and has a spherical structure, it is not easily worn away. Even if some PF-SiO2 is worn away during friction, it is continuously replenished by PF-SiO2 from other areas during subsequent wear cycles, thus greatly improving the wear resistance of the coating.

[0021] 2. Compared to the traditional SiO2 embedded in the binder structure formed by blending and spraying, this method adds semi-solid, dual-size nanoscale SiO2 containing ethanol to a polyolefin / butyl acetate solution. During stirring and curing, due to the different boiling points of ethanol and butyl acetate, ethanol evaporates faster than butyl acetate, resulting in phase separation. The POA microspheres partially dissolve and interconnect, leading to their aggregation. Furthermore, due to the evaporation of the organic solvent and the adhesion between the organic solvent and the inorganic nanoparticles, the PF-SiO2 nanoparticles tightly encapsulate the surface of the POA microspheres, forming a dense but rough surface at the nanoscale. This significantly improves the hydrophobicity of the superhydrophobic coating, achieving a contact angle of up to 160.6±1.0° and a sliding angle as low as 2.7±0.4°. Simultaneously, through a special preparation process, phase separation occurs during preparation, resulting in micron and nanoscale self-similar structures on the surface. Once the coating surface is damaged, the exposed new surface still possesses almost the same properties as the original surface, further significantly improving the coating's wear resistance.

[0022] 3. This method prepares dual-size ethanol-containing semi-solid PF-SiO2 nanoparticles, precisely controls their ratio with POA, and precisely controls the addition ratio between large-size and small-size semi-solid PF-SiO2 nanoparticles, so that the POA-based wear-resistant superhydrophobic coating exhibits excellent wear resistance and hydrophobic properties.

[0023] 4. This solution uses low-cost raw materials and does not rely on expensive instruments and equipment or complex processes. It has the advantages of simple operation and easy large-scale production, providing an economical and feasible technical path for the industrial preparation of wear-resistant superhydrophobic coatings.

[0024] 5. The coating made using this dual-size wear-resistant superhydrophobic material has self-cleaning and anti-fouling properties.

[0025] 6. The superhydrophobic coating made from this dual-size wear-resistant superhydrophobic material has high-temperature stability and still retains superhydrophobicity after being placed at a high temperature of 120-140℃ for 4 hours. Attached Figure Description

[0026] Figure 1 The image shows the water contact angle curves of coatings made of ethanol-containing semi-solid PF-SiO2 nanoparticles of two sizes with different proportions of POA after wear.

[0027] Figure 2 The graph shows the water contact angle curves of coatings with different proportions of large / small semi-solid PF-SiO2 nanoparticles and POA after wear.

[0028] Figure 3SEM images of this superhydrophobic coating at different magnifications.

[0029] Figure 4 The images show the adhesion evaluation test results of the superhydrophobic coating on the ABS sheet (a) and the magnesium alloy substrate (b).

[0030] Figure 5 This is a schematic diagram showing the contact angle of the superhydrophobic coating after immersion in 1M HCl (a) and 3.5wt% NaCl (b) solutions for 24 hours.

[0031] Figure 6 This is a graph showing the change in contact angle of the superhydrophobic coating before and after high-temperature testing.

[0032] Figure 7 The diagram shows the hydrophobic properties of the superhydrophobic coating on different substrates and its hydrophobic properties to various solutions.

[0033] Figure 8 This is a schematic diagram illustrating the self-cleaning and anti-fouling performance test of the superhydrophobic coating. Detailed Implementation

[0034] A dual-size wear-resistant superhydrophobic material based on phase separation method comprises dual-size ethanol-containing semi-solid PF-SiO2 nanoparticles, polyolefin adhesive (POA), and butyl acetate. The addition ratio of dual-size ethanol-containing semi-solid PF-SiO2 nanoparticles to polyolefin adhesive is 2.4–5.0, with the optimal ratio being 3.0–4.0. The amount of butyl acetate added is 3–6 times that of the dual-size ethanol-containing semi-solid PF-SiO2 nanoparticles. If there is too little butyl acetate, the suspension will be too thick and cannot be sprayed; if there is too much butyl acetate, there will be too much solvent, which may cause the coating to crack.

[0035] The dual-size ethanol-containing semi-solid PF-SiO2 nanoparticles include large-size and small-size semi-solid PF-SiO2 nanoparticles. The large-size semi-solid PF-SiO2 nanoparticles have a particle size of 100–200 nm; in this embodiment, a 100 nm particle size is used as an example, hereinafter referred to as PF-SiO2(100nm). The small-size semi-solid PF-SiO2 nanoparticles have a particle size of 10–20 nm; in this embodiment, a 12 nm particle size is used as an example, hereinafter referred to as PF-SiO2(12nm). The ratios PF-SiO2(100nm) / PF-SiO2(12nm) are 5:2, 5:3, 5:4, and 5:5, respectively.

[0036] Among them, the dual-size ethanol-containing semi-solid PF-SiO2 nanoparticles: POA = 3.0~4.0, and PF-SiO2(100nm) / PF-SiO2(12nm) = 5:4, the contact angle and wear resistance of the superhydrophobic coating can reach the optimal state.

[0037] The preparation method of dual-size wear-resistant superhydrophobic materials based on phase separation is as follows:

[0038] S1. Synthesis of dual-size ethanol-containing semi-solid PF-SiO2 nanoparticles

[0039] First, SiO2 nanoparticles with a diameter of 100 nm and 12 nm were synthesized separately. Taking PF-SiO2 (100 nm) as an example, the synthesis steps were as follows: 1 g of SiO2 (100 nm) nanoparticles were dispersed in 70 mL of ethanol solution (ethanol / water ratio: 2:3 / 2). The solution was then mechanically stirred for 15 min and sonicated for 15 min, followed by continuous stirring for 15 min. Then, 1.2 mL of 1H,1H,2H,2H-perfluorodecyltriethoxysilane (PFDTES) and 0.3 mL of tetraethyl orthosilicate (TEOS) were added, and the mixture was mechanically stirred for 2 h under indoor conditions to form a suspension. After centrifugation, semi-solid PF-SiO2 (100 nm) nanoparticles containing ethanol were obtained.

[0040] Semi-solid PF-SiO2 (12nm) nanoparticles containing ethanol were prepared according to the above synthesis steps.

[0041] Preparation of S2 and POA-based superhydrophobic coatings

[0042] First, 1.4 g of polyolefin adhesive (POA) was dissolved in 15.0 g of butyl acetate and mechanically stirred for 20 min. Then, 3.5 g of PF-SiO2 (100 nm) nanoparticles were slowly added while stirring. Subsequently, PF-SiO2 (12 nm) nanoparticles were added in ratios of PF-SiO2 (100 nm) / PF-SiO2 (12 nm) = 5:2, 5:3, 5:4, and 5:5. During this process, POA gradually underwent phase separation. The mixture was further stirred for 3 h to obtain a homogeneous POA / modified SiO2 suspension.

[0043] The POA / modified SiO2 suspension prepared above was sprayed onto an ABS board using a 0.2 MPa spray gun and cured at room temperature for 24 hours to prepare a phase-separated superhydrophobic coating. Coatings on other substrates were prepared using the same process.

[0044] experiment

[0045] I. Determining the mixing ratio between dual-size ethanol-containing semi-solid PF-SiO2 nanoparticles and polyolefin adhesive.

[0046] Among them, the dual-size ethanol-containing semi-solid PF-SiO2 nanoparticles, with PF-SiO2(100nm) / PF-SiO2(12) as the ratio, are...

[0047] Taking nm) = 5:2 as an example, the experiment is as follows:

[0048] 0.5 85.3 85.2 83.8 84.8 0.8 1 106.8 107.8 106.5 107.0 0.7 2 125.7 125.2 125.7 125.5 0.3 2.5 154.3 154.1 154.5 154.3 0.2 3.5 157.0 158.2 157.1 157.4 0.7 4.5 156.0 155.7 155.8 155.8 0.2 5.0 154.5 154.5 154.8 154.6 0.2 6.0 153.3 154.7 153.9 153.9 0.5

[0049] Table 1

[0050] 1. Hydrophobicity test results

[0051] As shown in Table 1, when PF-SiO2 / POA ≤ 2, the prepared coating is not a superhydrophobic coating. When PF-SiO2 / POA = 3.5, the contact angle of the coating is 157.4 ± 0.7°. When PF-SiO2 / POA = 5.0, the contact angle of the coating is 154.6 ± 0.2°, which is the highest. When PF-SiO2 / POA = 6.0, the contact angle of the coating is 153.9 ± 0.5°.

[0052] In summary, when PF-SiO2 / POA > 2, the prepared coating is a superhydrophobic coating. However, as the PF-SiO2 / POA ratio increases, the contact angle tends to decrease.

[0053] 2. Abrasion resistance test results

[0054] Taking three samples with PF-SiO2 / POA ratios of 3.5, 5.0, and 6.0 on ABS coatings as examples, using a 100g weight and 1000-grit sandpaper, the contact angle of the coating was measured after every 5 friction cycles. Figure 1 As shown.

[0055] For a coating with PF-SiO2 / POA = 3.5, after 25 wear cycles, the average contact angle of the coating was 148.6°, less than 150°. Subsequently, within 25–50 friction cycles, as the number of wear cycles increased, the average contact angle of the coating remained between 147.3° and 149.7°. Figure 1 (b)).

[0056] For a coating with PF-SiO2 / POA = 5.0, after 30 wear cycles, the average contact angle of the coating is less than 150°. Subsequently, with increasing wear cycles, the average contact angle again exceeds 150°, until after the 50th friction cycle, when the average contact angle reaches 146.5°, still exhibiting some hydrophobicity. Figure 1 (c)).

[0057] For the PF-SiO2 / POA = 6.0 coating, the average contact angle was less than 150° after 15 wear cycles. After the 20th wear cycle, the average contact angle again exceeded 150°. Subsequently, within 25-50 friction cycles, the average contact angle remained between 142.5° and 148.9° with increasing wear cycle count. Figure 1 (d)).

[0058] In summary, comparing the PF-SiO2 / POA ratios of 3.5, 5.0, and 6.0, the wear resistance of PF-SiO2 / POA ratios of 3.5 and 5.0 is similar, with contact angles of 149.7±0.7° and 146.5±2.4°, respectively, after 50 friction cycles. However, the wear resistance of PF-SiO2 / POA ratio 6.0 is weaker, with an average contact angle of 142.5±0.7° after 50 friction cycles. Therefore, as the PF-SiO2 / POA ratio increases, the wear resistance of the superhydrophobic coating gradually weakens due to the decrease in the relative content of POA.

[0059] II. Determine the ratio of PF-SiO2 (100nm) and PF-SiO2 (12nm).

[0060] After determining the appropriate ratio of PF-SiO2 and POA, the ratios of PF-SiO2 (100nm) and PF-SiO2 (12nm) were tested using the two ratios of PF-SiO2 / POA = 3.5 and 5.0 from Experiment 1 to obtain better hydrophobic and wear-resistant properties. See Tables 2 and 3 for details.

[0061] The wear resistance cycle refers to the number of friction cycles the coating undergoes before its contact angle fails. The standard for contact angle failure is: after several friction cycles, if the contact angle decreases by more than 10%, it is considered a contact angle failure.

[0062]

[0063]

[0064] Table 2 Contact Angle Data for PF-SiO2 / POA = 3.5 Dual-Size Superhydrophobic Coating

[0065]

[0066] Table 3. Contact angle data for PF-SiO2 / POA = 5.0 dual-size superhydrophobic coatings

[0067] 2.1 Hydrophobicity test results

[0068] As shown in Table 2, the contact angle of the coating increases as the addition ratio of SiO2 (12nm) gradually increases. The contact angle of the coating is the highest when the ratio of SiO2 (100nm): SiO2 (12nm) in the superhydrophobic coating is 5:4, which is 160.2±1.5°. However, when the addition ratio of the two is less than 5:4, the contact angle of the coating decreases.

[0069] As shown in Table 3, when the ratio of SiO2 (100nm):SiO2 (12nm) is 5:1, the contact angle of the coating is not as good as that of the single-size coating. When the ratio is <5:1, the wear resistance of the coating is significantly improved. Moreover, when the ratio of SiO2 (100nm):SiO2 (12nm) in the superhydrophobic coating is 5:4, the contact angle of the coating is the highest, at 155.9±0.9°. However, when the ratio of the two is <5:4, the contact angle of the coating begins to decrease.

[0070] 2.2 Abrasion resistance test results

[0071] Using a 100g weight and 1000-grit sandpaper, the contact angle of the coating was measured after every 5 friction cycles. The abrasion resistance of the two coatings was tested, and the test results are shown in Tables 2 and 3.

[0072] As can be seen from Tables 2 and 3, the ratio of SiO2 (100nm) to SiO2 (12nm) is crucial to the wear resistance of the coating. When the ratio is 5:1, the wear resistance is not as good as that of the single-size coating. When the ratio is <5:1, the wear resistance of the coating increases significantly with the increase of SiO2 (12nm). However, when the ratio is <5:4, the wear resistance of the coating begins to decrease, and the contact angle also begins to decrease.

[0073] When the ratio of SiO2(100nm):SiO2(12nm) in the coating is 5:4, its hydrophobic and wear-resistant properties are both at their optimal levels.

[0074] When the ratio of SiO2 (100nm):SiO2 (12nm) in PF-SiO2 (total) is 5:4, the two coatings with the ratio of PF-SiO2 (total):POA of 3.5 and 5.0 are named PF-SiO2(5:4) / POA=3.5 and PF-SiO2(5:4) / POA=5.0, respectively.

[0075] Figure 2 The wear resistance of two coatings, PF-SiO2(5:4) / POA=3.5 and PF-SiO2(5:4) / POA=5.0, was specifically demonstrated:

[0076] The PF-SiO2(5:4) / POA=3.5 coating had an average contact angle of less than 150° after 40 wear cycles, and maintained a high contact angle (149.1±0.3°) after 60 wear cycles, proving that the superhydrophobic coating still has good wear resistance.

[0077] The PF-SiO2(5:4) / POA=5.0 coating had an average contact angle of less than 150° after 15 sandpaper abrasion cycles, and a contact angle of 134.4±1.2° after 60 abrasion cycles.

[0078] This also shows that as the content of PF-SiO2 particles increases, the hydrophobicity of the coating may not necessarily increase, but the wear resistance of the coating will gradually decrease.

[0079] In summary, when the PF-SiO2 / POA ratio is 3.5 and the ratio of PF-SiO2 (100nm):PF-SiO2 (12nm) is 5:4, the coating exhibits the highest contact angle and the best wear resistance.

[0080] Figure 3 The images show scanning electron microscopy (SEM) images of the PF-SiO2(5:4) / POA=3.5 and PF-SiO2(5:4) / POA=5.0 coatings. Image 4(ae) shows the SEM images of the PF-SiO2(5:4) / POA=3.5 coating at different magnifications, and image 4(f) shows a cross-sectional view of the PF-SiO2(5:4) / POA=3.5 coating on the magnesium alloy surface. Figure 3 (gi) shows SEM images of the PF-SiO2 / POA=5.0 coating at different magnifications. The images show that during coating formation, due to the lower boiling point of ethanol compared to butyl acetate, micron-sized, irregularly shaped aggregates form on the surface of the aggregates during stirring and drying. Figure 3 (d, e) are bonded by POA adhesive. Furthermore, scanning electron microscopy was performed on the side surface of the PF-SiO2(5:4) / POA=3.5 coating, and the measured thickness was approximately 40–45 μm.

[0081] III. Coating Performance Testing

[0082] 1. Adhesion test

[0083] PF-SiO2 (5:4) / POA = 3.5 coatings were prepared on ABS and magnesium alloy substrates, respectively. An orthogonal grid cutting test was performed on the coating samples using a cross-cutting tool: first, a set of parallel cuts were made at 1 mm intervals, followed by the same number of cuts at the same intervals in the vertical direction. The adhesion level of the coating was quantitatively evaluated by calculating the ratio of the peeled area to the total test area. This method complies with the requirements of GB / T9286-2021 standard.

[0084] Use 3M tape to remove loose coating film from the cut surface. To ensure full contact between the 3M tape and the coating surface, roll a 100g weight on the tape. After applying the tape, hold the unsupported end and gently peel it off.

[0085] like Figure 4 As shown, the PPF-SiO2(5:4) / POA=3.5 coating exhibits good adhesion on both glass and magnesium alloy substrates. Comparison with the test results rating shows the coating's adhesion level is Grade 1. Furthermore, even after the adhesion evaluation, water droplets remain non-wetting on the surface, indicating that the coating still maintains good hydrophobicity.

[0086] 2. Coating stability and universality testing

[0087] 2.1 Chemical stability of superhydrophobic coatings

[0088] Depend on Figure 5 It can be seen that the PF-SiO2(5:4) / POA=3.5 superhydrophobic coating has strong chemical stability. After being placed in 1MHCl and 3.5wt%NaCl solutions for 24 hours, the contact angles are 158.6±0.7° and 161.3±0.4°, respectively, and the coating still exhibits good superhydrophobic properties.

[0089] 2.2 High-temperature stability of the coating

[0090] A PF-SiO2(5:4) / POA=3.5 coating was prepared on the surface of a magnesium alloy substrate, and the water contact angle was measured before and after being placed at 120℃, 140℃, 160℃ and 180℃ for 4 hours.

[0091] Depend on Figure 6It can be seen that after being placed at 120℃ and 140℃ for 4 hours, the contact angle of the PF-SiO2(5:4) / POA=3.5 coating remained essentially unchanged, indicating that the surface structure of the coating and the hydrophobicity of PF-SiO2 remained unchanged at 120℃ and 140℃, resulting in a basically constant contact angle. After being placed at 160℃ for 4 hours, the contact angle of the PF-SiO2(5:4) / POA=3.5 coating decreased from 161.1±0.6° to 155.8±0.9°, and after being placed at 180℃ for 4 hours, the contact angle of the PF-SiO2(5:4) / POA=3.5 coating decreased from 160.5±0.9° to 148.0±0.9°. In summary, the PF-SiO2(5:4) / POA=3.5 superhydrophobic coating exhibits high-temperature stability, retaining its superhydrophobicity even after being placed at 120–140℃ for 4 hours, demonstrating strong potential application value.

[0092] 3. The universality of the coating

[0093] Figure 7 PF-SiO2 (5:4) / POA = 3.5 coatings were prepared on glass (a), magnesium alloy (b), ABS board (d), and paper (e) substrates, respectively. The PF-SiO2 (5:4) / POA = 3.5 coatings exhibited superhydrophobic properties on all these substrates, and also showed good hydrophobicity to water, cola, juice, and yogurt. Figure 7 (c, f)).

[0094] 4. The coating's self-cleaning and anti-fouling properties

[0095] Methylene blue was placed on the surface of the PF-SiO2(5:4) / POA=3.5 coating. Figure 8 (a1-a4)), gravel Figure 8 (b1-b4)) Tilting the surface at a certain angle, water is dripped from above the coating. It can be seen that methylene blue and grit are left with the water droplets, and the coating surface is restored to cleanliness. Figure 8 (a1-b4) demonstrates that the coating surface possesses self-cleaning properties similar to the "lotus effect." Furthermore, when the coating is immersed in a deionized methylene blue solution and then removed, the superhydrophobic surface remains clean, while the back of the ABS board is contaminated with the methylene blue solution, proving that the superhydrophobic surface has a certain degree of anti-fouling performance. Figure 8 (c1-c4)).

[0096] The above descriptions are merely embodiments of the present invention, and common knowledge such as specific technical solutions and / or characteristics are not described in detail here. It should be noted that those skilled in the art can make various modifications and improvements without departing from the technical solutions of the present invention, and these should also be considered within the scope of protection of the present invention. These modifications and improvements will not affect the effectiveness of the implementation of the present invention or the practicality of the patent. The scope of protection claimed in this application should be determined by the content of its claims, and the specific embodiments described in the specification can be used to interpret the content of the claims.

Claims

1. A dual-size wear-resistant superhydrophobic material based on phase separation method, characterized in that: The product comprises dual-size ethanol-containing semi-solid PF-SiO2 nanoparticles, polyolefin adhesive, and butyl acetate. The dual-size ethanol-containing semi-solid PF-SiO2 nanoparticles include large-size and small-size semi-solid PF-SiO2 nanoparticles. The addition ratio of the dual-size ethanol-containing semi-solid PF-SiO2 nanoparticles to the polyolefin adhesive is 2.4~5.0, and the ratio of large-size to small-size semi-solid PF-SiO2 nanoparticles is 5:(2~5). The particle size of the large-size semi-solid PF-SiO2 nanoparticles is 100~200 nm, and the particle size of the small-size semi-solid PF-SiO2 nanoparticles is 10~20 nm. The preparation method of the dual-size ethanol-containing semi-solid PF-SiO2 nanoparticles is as follows: two types of SiO2 nanoparticles with different particle sizes are synthesized separately. The synthesis steps are as follows: after mixing SiO2 nanoparticles with ethanol solution evenly, sodium methylsilicate is added and stirred evenly, 1H,1H,2H,2H-perfluorodecyltriethoxysilane (PFDTES) and tetraethyl orthosilicate are added and mechanically stirred to form a suspension. The suspension is centrifuged to obtain ethanol-containing semi-solid PF-SiO2 nanoparticles.

2. The method for preparing a dual-size wear-resistant superhydrophobic material based on phase separation according to claim 1, characterized in that: Includes the following steps: S1. Synthesis of dual-size ethanol-containing semi-solid PF-SiO2 nanoparticles: Two types of SiO2 nanoparticles with different particle sizes were synthesized separately. The synthesis steps were as follows: SiO2 nanoparticles were mixed with ethanol solution, sodium methylsilicate was added and stirred evenly, 1H,1H,2H,2H-perfluorodecyltriethoxysilane (PFDTES) and tetraethyl orthosilicate were added and mechanically stirred to form a suspension. The suspension was centrifuged to obtain ethanol-containing semi-solid PF-SiO2 nanoparticles. S2. Dissolve polyolefin adhesive (POA) in butyl acetate and stir for 20-25 min. Then, while stirring, add large-sized semi-solid PF-SiO2 nanoparticles and small-sized semi-solid PF-SiO2 nanoparticles and stir for 3-3.5 h to obtain a POA / modified SiO2 suspension.

3. The method for preparing a dual-size wear-resistant superhydrophobic material based on phase separation according to claim 2, characterized in that: In step S1, the addition ratio of SiO2 nanoparticles to ethanol solution is 1g:(65-75)ml; the ethanol solution includes 23 parts ethanol and 2 parts water.

4. A method for preparing a dual-size wear-resistant superhydrophobic material based on phase separation according to claim 3, characterized in that: In step S1, the mass ratio of SiO2 nanoparticles: sodium methylsilicate: PFDTES: tetraethyl orthosilicate is 1:0.3:(1.63 ~1.67):0.

28.

5. A method for preparing a dual-size wear-resistant superhydrophobic material based on phase separation according to claim 4, characterized in that: In step S1, the SiO2 nanoparticles are mixed with the ethanol solution by mechanical stirring for 15 min and ultrasonic treatment for 15 min in sequence.

6. The application of a dual-size wear-resistant superhydrophobic material based on phase separation method as described in claim 1, characterized in that: Its application in the coatings field involves spraying the dual-size wear-resistant superhydrophobic material onto the substrate using a spray gun, and then curing it at room temperature for 24 hours to obtain a phase-separated superhydrophobic coating.

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