Super-hydrophobic film with photo-thermal ice preventing and removing performance and preparation method of super-hydrophobic film

Abstract

The invention belongs to the technical field of photo-thermal super-hydrophobic films, and discloses a super-hydrophobic film with photo-thermal ice preventing and removing performance and a preparation method of the super-hydrophobic film. The super-hydrophobic thin film is obtained by treating a composite thin film solution through a non-solvent induced phase separation method and a nano laser etching technology, and the composite thin film solution comprises phthalazinone polyarylether sulfone ketone, polydimethylsiloxane, nano molybdenum disulfide and N-methyl pyrrolidone. The preparation method comprises the following steps: dissolving phthalazinone polyarylether sulphone ketone in N-methyl pyrrolidone, and cooperating with nano molybdenum disulfide to prepare the photo-thermal super-hydrophobic anti-icing and deicing film. The anti-icing and deicing film material prepared by the preparation method disclosed by the invention realizes the functions of superhydrophobicity on the upper side and heat insulation on the lower side through surface laser etching, has excellent photo-thermal performance in a full-spectrum region of sunlight, and can achieve an anti-icing and deicing effect under the irradiation of 0.1 sunlight intensity at the temperature of 20 DEG C below zero.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of photothermal super-hydrophobic film, and relates to a super-hydrophobic film with photothermal anti-icing performance and a preparation method thereof. BACKGROUND

[0002] Ice accretion poses a universal threat to modern infrastructure, causing aircraft to crash-land, power systems to collapse, or polar energy systems to fail, resulting in more than 12 billion US dollars of loss each year. Traditional countermeasures are divided into two categories: energy-consuming active methods (such as electric heating deicing, consuming 300-800 W / m 2 ) and passive coatings using super-hydrophobicity or low-surface-energy elastomers. Among them, the former puts pressure on the energy budget, while the latter is ineffective in continuous freezing rain or dark environments. Photothermal anti-icing surfaces, as a sustainable alternative, generate interfacial heat by utilizing sunlight, thereby delaying ice nucleation and reducing adhesion, which has broad application prospects in sunny environments.

[0003] Current photothermal icephobic surfaces mainly target planar geometries, using carbon-based composites, protruding nanowire arrays, or recessed microcavities, to maximize solar absorption under near-normal incidence. However, these surfaces still face severe challenges in low-irradiance extreme environments such as polar winter, high-altitude flight, or overcast days: (1) Angle attenuation: Micro / nano textures optimized for 0° light incidence will suffer a significant loss of absorption due to geometric shadowing effects above 45° tilt angle, with recessed structures performing the worst due to trapped photons dissipating heat through the sidewalls; (2) The combination of low winter solar elevation angle and atmospheric attenuation reduces the ground solar intensity to 0.5-0.7 sun at noon, and especially in the morning / evening period, the irradiance is further reduced to about 0.1 sun. At this low irradiance, the path of sunlight through the Earth's atmosphere is significantly longer than at noon, and under such low irradiance conditions, the temperature rise generated by traditional planar absorbers is not enough to suppress ice nucleation, and in curved structures (pipes, cables), this limitation is catastrophically amplified due to radial heat dissipation; (3) Thermal loss: High-absorption micro / nano structures (>90%) accelerate heat loss to the metal substrate, offsetting the interfacial heating effect. Even with excellent photothermal materials, the problem of solar angle sensitivity and heat loss in real scenarios cannot be solved, resulting in non-planar systems that cannot resist all-around icing under weak light. Therefore, the current reported "Robust photothermal icephobic surface with mechanical durability of multi-bioinspired structures" (Advanced Materials 2024, 36:2305322) and "Scalable robust photothermal uperhydrophobic coatings for efficient nti-icing and de-icing in simulated / real nvironments" (Nature Communications 2024, 15:9610) and other documents cannot ensure stable anti-icing performance under large-angle solar incidence. SUMMARY

[0004] The purpose of the present application is to overcome the above-mentioned limitations of existing photothermal superhydrophobic surfaces in terms of anti-icing performance under large-angle solar incidence, and to provide a superhydrophobic film with active / passive combination and photothermal anti-icing performance and a preparation method thereof.

[0005] The technical scheme of the present application is:

[0006] A superhydrophobic film with photothermal anti-icing performance is obtained by film forming treatment of a composite film solution;

[0007] The composite film solution comprises heteronaphthalene polyphenyl ether sulfone ketone, polydimethylsiloxane, nano molybdenum disulfide and N-methyl pyrrolidone, and the mass percentage of each component is as follows:

[0008] Heteronaphthalene polyphenyl ether sulfone ketone: polydimethylsiloxane: nano molybdenum disulfide: N-methyl pyrrolidone = 1: 0.1-0.5: 0.005-0.02: 4-10.

[0009] A preparation method of a super-hydrophobic film with photo-thermal anti-icing performance, the steps are as follows:

[0010] Step 1, dissolve heteronaphthalene polyphenyl ether sulfone ketone in N-methyl pyrrolidone, then add polydimethylsiloxane, stir and mix, then add nano molybdenum disulfide dispersion, stir and mix to obtain a composite film solution;

[0011] Step 2, immerse the composite film solution in step 1 in deionized water for 48h after film formation by the blade coating method to perform non-solvent induced phase separation, to obtain a composite film surface;

[0012] Step 3, design micro-nano structure on the composite film surface in step 2 by nanosecond laser etching technology to obtain a super-hydrophobic film with photo-thermal anti-icing performance; the parameters of the micro-nano structure design are as follows:

[0013] Laser frequency: 5-20KHz; current: 0.1-2A; scanning speed: 50-1000mm / s; laser scanning interval: 0.005-0.1mm; scanning track: net format and cylindrical type.

[0014] The innovation of the present application: the present application constructs a stable super-hydrophobic upper surface and a heat-insulating lower surface on the heteronaphthalene polyphenyl ether sulfone ketone / polydimethylsiloxane film by the method of non-solvent induced phase separation combined with laser etching, thereby realizing passive anti-icing function under no light condition. In addition, the photo-thermal synergistic effect between heteronaphthalene polyphenyl ether sulfone ketone material and nano molybdenum disulfide can realize full-spectrum (250-2025nm) solar light absorption. Combined with the micro-nano structure formed on the surface after laser etching, the present application can realize excellent anti-icing effect under the condition of low light intensity (0.1 sun) and solar light incident angle 0-60°.

[0015] The beneficial effects of the present application are as follows:

[0016] (1) The present application uses heteronaphthalene polyphenyl ether sulfone ketone and polydimethylsiloxane as a stable film matrix, constructs micro-nano structure on the upper surface and lower surface of the film by the method of non-solvent induced phase separation and nanosecond laser etching technology, so that the composite film has super-hydrophobicity and heat insulation at the same time, and can realize excellent delayed icing function under no light condition;

[0017] (2) The application has both light-heat active deicing ability and existing anti-icing super-hydrophobic film, uses the light-heat synergistic effect of hetero-naphthalene diphenyl polyarylether sulfone ketone and nano-molybdenum disulfide to absorb full-spectrum sunlight, combines laser etching to have excellent absorption capacity, can convert solar energy into heat energy, and raise the surface temperature to realize long-term effective anti-icing. Most importantly, the special surface structure design of the application has low environmental dependence, still has good deicing effect under low light intensity and large-angle oblique light source conditions, and has good potential application value.

[0018] (3) The active / passive combined light-heat super-hydrophobic film prepared by the application has diversified preparation methods, can be sprayed, blade coated, etc., has simple process, convenient operation, is suitable for large-area large-scale construction, and is easy to construct on different object surfaces. BRIEF DESCRIPTION OF DRAWINGS

[0019] Figure 1 It is a surface morphology diagram of the film of Example 1, wherein (a) is a macro photograph, and (b) is a scanning electron micrograph.

[0020] Figure 2 It is a surface morphology diagram of the film of Example 2, wherein (a) is a macro photograph, and (b) is a scanning electron micrograph.

[0021] Figure 3 It is a surface contact angle comparison diagram of the anti-icing film prepared under different polydimethylsiloxane addition amounts and laser scanning distances, wherein (a) is Example 1, and (b) is Example 2.

[0022] Figure 4 It is the ultraviolet-visible-near-infrared absorption spectrum of the anti-icing film prepared in Example 1, 2 and Comparative Example 1. DETAILED DESCRIPTION

[0023] The specific embodiments of the application are further illustrated below in combination with the drawings and technical solutions.

[0024] Example 1

[0025] The embodiment provides a super-hydrophobic film with light-heat anti-icing performance, which is obtained by film forming treatment of a composite film solution:

[0026] The composite film solution comprises hetero-naphthalene diphenyl polyarylether sulfone ketone, polydimethylsiloxane, nano-molybdenum disulfide and N-methyl pyrrolidone, and the mass percentage of each component is as follows:

[0027] Hetero-naphthalene diphenyl polyarylether sulfone ketone: polydimethylsiloxane: nano-molybdenum disulfide: N-methyl pyrrolidone = 1: 0.1-0.5: 0.005-0.02: 4-10.

[0028] The preparation method of the above-mentioned film comprises the following steps:

[0029] (1) 1 g of heteronaphthalene-biphenyl polyarylether sulfone ketone is dissolved in 5 mL of N-methyl pyrrolidone, and stirred at room temperature until completely dissolved to obtain a heteronaphthalene-biphenyl polyarylether sulfone ketone solution. Then, 0.2 g of polydimethylsiloxane is added to the heteronaphthalene-biphenyl polyarylether sulfone ketone solution, and stirred at room temperature for 1 h. Then, 0.01 g of nano-molybdenum disulfide in a dispersion liquid obtained by ultrasonic treatment is added, and continuously stirred at room temperature by magnetic force for 1 h to obtain a composite film solution.

[0030] (2) The composite film solution in step (1) is prepared into a composite film by a non-solvent induced phase separation method: the composite solution is coated by using a 400 μm doctor blade, and then soaked in deionized water for 48 h, during which the water is replaced twice, and dried at 60°C for 12 h to evaporate the solvent, so as to form a film with a thickness of about 200 μm.

[0031] (3) The composite film in step (2) is designed with a micro-nano structure on the upper surface by a nanosecond laser etching technology, and the laser frequency is set to 20 KHz; the current is 1 A; the scanning speed is 500 mm / s; and the laser scanning interval is 0.005-0.1 mm. In this embodiment, the laser scanning pattern trajectory used in the present application is a net format and a cylindrical type, and the net format is selected in this embodiment.

[0032] The photo-thermal super-hydrophobic film prepared in this embodiment exhibits a uniform protruding micro-nano structure, as shown in Figure 1 .

[0033] Example 2

[0034] This embodiment provides a super-hydrophobic film with photo-thermal anti-icing performance, which is obtained by film forming treatment of a composite film solution:

[0035] The composite film solution comprises heteronaphthalene-biphenyl polyarylether sulfone ketone, polydimethylsiloxane, nano-molybdenum disulfide and N-methyl pyrrolidone, and the mass percentage of each component is as follows:

[0036] Heteronaphthalene-biphenyl polyarylether sulfone ketone: polydimethylsiloxane: nano-molybdenum disulfide: N-methyl pyrrolidone = 1: 0.1-0.5: 0.005-0.02: 4-10.

[0037] The preparation method of the above-mentioned film comprises the following steps:

[0038] (1) 1 g of heteronaphthalene-biphenyl polyarylether sulfone ketone was dissolved in 5 mL of N-methyl pyrrolidone, and stirred at room temperature until completely dissolved to obtain a heteronaphthalene-biphenyl polyarylether sulfone ketone solution, then 0.2 g of polydimethylsiloxane was added to the heteronaphthalene-biphenyl polyarylether sulfone ketone solution, and stirred at room temperature for 1 h, then 0.01 g of nano-molybdenum disulfide-containing dispersion liquid obtained by ultrasonic treatment was added, and continuously stirred at room temperature for 1 h to obtain a composite film solution.

[0039] (2) The composite film solution in step (1) was prepared into a composite film by a non-solvent induced phase separation method: the composite solution was coated by using a 400 μm doctor blade, then soaked in deionized water for 48 h, during which the water was changed twice, and dried at 60°C for 12 h to evaporate the solvent, to form a film with a thickness of about 200 μm.

[0040] (3) The composite film in step (2) was designed with micro-nano structures on the upper surface by a nanosecond laser etching technology, the laser frequency was set to 20 KHz; current: 1 A; scanning speed: 500 mm / s; laser scanning interval: 0.005-0.1 mm. Among them, the laser scanning pattern trajectory used in the present application has a net format and a cylindrical type, and the cylindrical type is selected in this embodiment.

[0041] The photo-thermal super-hydrophobic film prepared in this embodiment exhibits a uniform concave micro-nano structure, as shown in Figure 2 .

[0042] Example 3

[0043] The present embodiment provides a super-hydrophobic film with photo-thermal anti-icing performance, which is prepared from a composite film solution by film forming treatment:

[0044] The composite film solution includes heteronaphthalene-biphenyl polyarylether sulfone ketone, polydimethylsiloxane, nano-molybdenum disulfide and N-methyl pyrrolidone, and the mass percentage of each component is as follows:

[0045] Heteronaphthalene-biphenyl polyarylether sulfone ketone: polydimethylsiloxane: nano-molybdenum disulfide: N-methyl pyrrolidone = 1: 0.1-0.5: 0.005-0.02: 4-10.

[0046] The preparation method of the above-mentioned film comprises the following steps:

[0047] (1) 1 g of heteronaphthalene-biphenyl polyarylether sulfone ketone was dissolved in 5 mL of N-methyl pyrrolidone, and stirred at room temperature until completely dissolved to obtain a heteronaphthalene-biphenyl polyarylether sulfone ketone solution, then 0.2 g of polydimethylsiloxane was added to the heteronaphthalene-biphenyl polyarylether sulfone ketone solution, and stirred at room temperature for 1 h, then 0.01 g of nano-molybdenum disulfide-containing dispersion liquid obtained by ultrasonic treatment was added, and continuously stirred at room temperature for 1 h to obtain a composite film solution.

[0048] (2) The composite film solution in step (1) is prepared into a composite film by a non-solvent induced phase separation method: the composite solution is coated by using a 400 pm doctor blade, then soaked in deionized water for 48 h, during which the water is replaced twice, and dried at 60 °C for 12 h to evaporate the solvent, forming a film with a thickness of about 200 pm.

[0049] (3) The composite film in step (2) is designed with micro-nano structures on the upper and lower surfaces by a nanosecond laser etching technology, with a laser frequency of 20 KHz; current: 1 A; scanning speed: 500 mm / s; laser scanning interval: 0.005-0.1 mm. Among them, the laser scanning pattern trajectory used in the present application has a mesh format and a cylindrical type, and the cylindrical type is selected for etching the upper surface of the film, and the mesh format is selected for etching the lower surface of the film.

[0050] Comparative Example 1

[0051] Comparative Example 1 is a heteronaphthalene polyphenyl ether sulfone ketone / polydimethylsiloxane / nano-molybdenum disulfide composite film, which is prepared by using basically the same preparation process as Example 1, with the difference that only steps (1) and (2) are performed, and step (3) is not performed.

[0052] Comparative Example 2

[0053] Comparative Example 2 is a heteronaphthalene polyphenyl ether sulfone ketone / polydimethylsiloxane / nano-molybdenum disulfide composite film, which is prepared by using basically the same preparation process as Example 1, with the difference that the composite film solution obtained in step (1) is directly dried at 220 °C for 12 h to remove the solvent after being coated by using a 400 pm doctor blade, and then step (3) is performed.

[0054] Comparative Example 3

[0055] Comparative Example 3 is a heteronaphthalene polyphenyl ether sulfone ketone / polydimethylsiloxane / nano-molybdenum disulfide composite film, which is prepared by using basically the same preparation process as Example 1, with the difference that no heteronaphthalene polyphenyl ether sulfone ketone material is added in step (1), and the remaining steps remain unchanged.

[0056] Reference Figure 3Comparing the contact angles of the upper surfaces of the films prepared in Examples 1 and 2 under different amounts of polydimethylsiloxane addition and laser scanning distances, it was found that when the amount of polydimethylsiloxane addition was 20% and the scanning distance was 0.02 mm, the water contact angles of Examples 1 and 2 could reach 154.8° and 158.7°, respectively, while the water contact angles of Comparative Examples 1, 2 and 3 were only 109.2°, 80.1° and 120.3°, respectively. This is because the polydimethylsiloxane imparts a certain hydrophobicity to the substrate, and after laser etching of the sub-micron rough pore structure, air molecules are physically trapped therein to form a stable air-liquid composite interface, thereby achieving superhydrophobicity. Comparative Example 1 without the non-solvent induced phase separation step lacks internal pores, and even after laser etching, the surface wettability is severely insufficient; Comparative Example 3 even lacks the polyphenylsulfone ketone of poly naphthalene biphenyl aryl ether, resulting in poor stability and damage to the film surface during laser etching. At the same time, the thermal conductivity test of the films of Examples 1, 2 and 3 found that the thermal conductivities of the three were 0.171 W m -1 K -1 , 0.108 W m -1 K -1 and 0.051 W m -1 K -1 , respectively. The above results show that through the synergistic design of the micro-nano structure of the upper and lower surfaces of the film, superhydrophobicity and thermal insulation are simultaneously achieved, which enables the film prepared in Example 3 to have excellent delayed icing performance, and the freezing time of the water droplets (50 μL) on the surface is extended to 751.5 s in a dark environment at -10°C / 80% RH, which is 12.8 times more effective than a metal surface.

[0057] See Figure 4UV-Vis-NIR absorption spectra of the films prepared for Example 1, 2 and Comparative Example 1. As can be seen from the figure, the surfaces of Example 1, 2 constructed by laser etching technology have excellent absorption performance in the ultraviolet and near-infrared regions of the solar spectrum, while Comparative Example 1 is relatively poor, because the multi-level structure constructed by laser etching enhances the light trapping ability (multiple reflection absorption), and the carbonization of the surface improves the wide-spectrum light absorption efficiency of the material. In addition, Comparative Example 3 will cause the film to have poor absorption performance in the ultraviolet-near-infrared region of the solar spectrum due to the absence of polyarylether sulfone ketone of polyarylate-biphenyl. At the same time, Example 1 has better absorption performance than Example 2 in the surface of the oblique light, because the recessed structure of Example 1 will have a shadow effect when facing the oblique light, while the protruding micro-nano pore structure of Example 2 can maximize the use of oblique light through its own geometric light guiding effect. Comparative Example 2 lacks internal pores due to the lack of the key step of non-solvent induced phase separation, so its absorption performance is insufficient when facing vertical or oblique light. Similarly, this makes Example 3 have excellent ice melting performance under low light and large angle solar light source conditions. Under the conditions of 0.1 sun, 60° incidence, the surface ice crystals at -20℃ can be completely melted and removed within 30 min.

Claims

1. A superhydrophobic thin film with photothermal anti-icing and de-icing properties, characterized in that, This superhydrophobic film with photothermal anti-icing and de-icing properties is obtained by film formation treatment of a composite film solution.

2. The superhydrophobic film with photothermal anti-icing and de-icing properties according to claim 1, characterized in that, The composite film solution includes naphthalene-biphenyl polyarylether sulfone ketone, polydimethylsiloxane, molybdenum disulfide nanoparticles, and N-methylpyrrolidone.

3. The superhydrophobic film with photothermal anti-icing and de-icing properties according to claim 2, characterized in that, The mass percentages of each component in the composite thin film solution are as follows: Naphthyl biphenyl polyarylether sulfone ketone: polydimethylsiloxane: nano molybdenum disulfide: N-methylpyrrolidone = 1: 0.1~0.5: 0.005~0.02: 4~10.

4. A method for preparing a superhydrophobic thin film with photothermal anti-icing and de-icing properties as described in claim 3, characterized in that, The steps are as follows: Step 1: Dissolve polyarylene ether sulfone ketone in N-methylpyrrolidone, then add polydimethylsiloxane, stir and mix, then add nano molybdenum disulfide dispersion, stir and mix to obtain composite film solution; Step 2: After the composite film solution in Step 1 is formed into a film by the scraping method, it is immersed in deionized water for 48 hours to exchange solvent and obtain the surface of the composite film. Step 3: The surface of the composite film in Step 2 is designed with micro-nano structures using nanosecond laser etching technology to obtain a superhydrophobic film with photothermal anti-icing properties.

5. The preparation method according to claim 4, characterized in that, The parameters for the micro / nano structure design are as follows: Laser frequency: 5-20KHz; current: 0.1-2A; scanning speed: 50-1000mm / s; laser scanning spacing: 0.005-0.1mm; scanning trajectory: grid and cylindrical.

6. The preparation method according to claim 4, characterized in that, The substrate can be a flexible substrate or a rigid substrate.

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