Material with micro-nano structure surface and processing method thereof

Abstract

This invention provides a material with a micro / nanostructured surface and a method for processing the same. The micro / nanostructure includes nanoprotrusions and microgrooves disposed on the material surface. The height of the nanoprotrusions is 0-120 nm, the bottom diameter is 500-1000 nm, the groove depth is 15-70 μm, and the groove width is 20-60 μm. The spacing between adjacent grooves is 0.1 mm-3 mm, and the number of nanoprotrusions within a grid formed by two sets of adjacent grooves is 30,000-400,000. The bearing steel sheet with a micro / nanostructure obtained by the method of this invention exhibits high adhesion and superhydrophobic properties, as well as good mechanical wear resistance.

Description

Technical Field

[0001] This invention relates to the field of laser near-field processing technology, specifically to a material with a micro / nano structured surface and its processing method. Background Technology

[0002] In recent years, inspired by the biological characteristics of nature, research on micro- and nano-patterned surfaces has received considerable attention and has been widely applied in practical engineering. Examples include anti-reflection structures for solar panels, coloring, anti-icing surfaces, self-cleaning surfaces, fluid transport, and SERS substrate fabrication, demonstrating broad application prospects.

[0003] Researchers have made considerable efforts in the fabrication of hydrophobic micro / nano composite structures, with commonly used techniques including electrodeposition, chemical deposition, selective mask deposition, and laser direct writing. However, these methods have limitations such as high cost or environmental pollution due to the use of excessive amounts of harmful chemical reagents, as well as relatively low optical imaging resolution. In contrast, laser near-field processing technology allows microspheres to manipulate light in a novel way that traditional optical elements cannot achieve, realizing sub-100nm feature sizes. Furthermore, laser near-field processed micro / nano structures offer controllability and high efficiency, enabling programmed and large-area processing, and are environmentally friendly, increasing both hydrophobicity and wear resistance.

[0004] In view of the above reasons, this invention is proposed. Summary of the Invention

[0005] One object of the present invention is to provide a material having a micro / nano structured surface;

[0006] Another object of the present invention is to provide a method for processing the surface of micro / nano structures of materials.

[0007] Another object of the present invention is to provide a material with a micro / nano structured surface obtained by the aforementioned processing method.

[0008] To achieve the above objectives, in one aspect, the present invention provides a material with a micro / nano structure surface, wherein the micro / nano structure includes nano-protrusions and micro-grooves disposed on the surface of the material, the height of the nano-protrusions is 20-120 nm, the bottom diameter is 500-1000 nm, the groove depth is 15-70 μm, and the groove width is 20-60 μm; the spacing between adjacent grooves is 0.1 mm-3 mm, and the number of nano-protrusions in the grid formed by two sets of adjacent grooves is 3w-400w.

[0009] According to some specific embodiments of the present invention, the material is a metal (sheet, strip, or block material, such as metal sheet, metal strip, or metal block).

[0010] According to some specific embodiments of the present invention, the material is steel, aluminum, silicon or copper.

[0011] According to some specific embodiments of the present invention, the material is bearing steel.

[0012] According to some specific embodiments of the present invention, the material is 9Cr18 bearing steel.

[0013] On the other hand, the present invention also provides a method for processing the surface of a material micro / nano structure, the method comprising:

[0014] The steps of depositing a silica microsphere film on the surface of the material and processing micro / nano structures on the surface of the material with the silica microsphere film deposited using a laser;

[0015] The step of depositing a silica microsphere film on the surface of the material includes the following steps: preparing an alcohol-water dispersion of silica microspheres; adding the silica microsphere alcohol-water dispersion to water to obtain a dispersion system and adding sodium dodecylbenzenesulfonate hydrogel blocks to induce the liquid-gas interfacial tension gradient field of the system; obtaining a silica microsphere film through self-assembly of silica microspheres; and applying the silica microsphere film to the surface of the material.

[0016] The volume ratio of water to alcohol in the alcohol-water dispersion is 1:9 to 1:1.

[0017] This invention utilizes the liquid-gas interfacial tension gradient field induced by sodium dodecylbenzenesulfonate hydrogel blocks to place the sodium dodecylbenzenesulfonate hydrogel blocks in a dispersion system (a system composed of silica microsphere dispersion and water) for a period of time (2-60 seconds, preferably 2-10 seconds), and then remove them.

[0018] The sodium dodecylbenzenesulfonate hydrogel block of the present invention can be reused after removal.

[0019] This invention induces silica microspheres to self-assemble and efficiently and orderly arrange into a single-layer film by inducing the formation of sodium dodecylbenzenesulfonate hydrogel blocks.

[0020] According to some specific embodiments of the present invention, the silica microsphere alcoholic aqueous dispersion is added to water at a uniform and stable rate.

[0021] According to some specific embodiments of the present invention, the particle size of the silica microspheres is 0.5 to 5 μm.

[0022] According to some specific embodiments of the present invention, the particle size of the silica microspheres is 0.6 to 4 μm.

[0023] According to some specific embodiments of the present invention, the particle size of the silica microspheres is 0.75 to 3 μm.

[0024] According to some specific embodiments of the present invention, the volume ratio of water to alcohol in the alcohol-water dispersion is 1.5:8.5 to 4.5:5.5.

[0025] According to some specific embodiments of the present invention, the volume ratio of water to alcohol in the alcohol-water dispersion is 2:8 to 4:6.

[0026] According to some specific embodiments of the present invention, the silicon dioxide is hydrophobic silicon dioxide with a contact angle of 120° to 140°.

[0027] According to some specific embodiments of the present invention, the mass concentration of silica is 1.5 to 3.5 wt%, based on the total mass of the alcohol-water dispersion of the silica microspheres as 100%.

[0028] According to some specific embodiments of the present invention, the addition of the silica microsphere alcohol aqueous dispersion to water is carried out at a ratio of dispersion to water of 1 / 1200 to 1 / 600.

[0029] According to some specific embodiments of the present invention, the sodium dodecylbenzenesulfonate hydrogel block is prepared by a method comprising the following steps:

[0030] Sodium dodecylbenzenesulfonate, acrylamide, and N,N'-methylenebisacrylamide were used as raw materials. A crosslinking reaction was carried out in deionized water in the presence of ammonium persulfate and N,N,N',N'-tetramethylenediamine to obtain the sodium dodecylbenzenesulfonate hydrogel block. The mass ratio of sodium dodecylbenzenesulfonate, acrylamide, N,N'-methylenebisacrylamide, ammonium persulfate, N,N,N',N'-tetramethylenediamine, and deionized water was (0.1-15):(0.1-20):(0.001-6):(0.001-3):(0.001-5):(1-30). The crosslinking reaction was carried out at 20-90℃ for 8-15 h.

[0031] According to some specific embodiments of the present invention, the mass ratio of sodium dodecylbenzenesulfonate, acrylamide, N,N'-methylenebisacrylamide, ammonium persulfate, N,N,N',N'-tetramethylenediamine and deionized water is (0.5-12):(0.5-16):(0.005-5):(0.005-2):(5-26):(0.002-4).

[0032] According to some specific embodiments of the present invention, the mass ratio of sodium dodecylbenzenesulfonate, acrylamide, N,N'-methylenebisacrylamide, ammonium persulfate, N,N,N',N'-tetramethylenediamine and deionized water is (1-9):(1-12):(0.012-3):(0.01-1.5):(0.003-3):(8-24).

[0033] According to some specific embodiments of the present invention, the crosslinking reaction is carried out at 20-80°C for 9-14 hours.

[0034] According to some specific embodiments of the present invention, the crosslinking reaction is carried out at 25–50°C for 9.5–13 hours.

[0035] According to some specific embodiments of the present invention, the sodium dodecylbenzenesulfonate hydrogel block is prepared by a method comprising the following steps:

[0036] Sodium dodecylbenzenesulfonate, acrylamide, and N,N'-methylenebisacrylamide were used as raw materials. In the presence of ammonium persulfate and N,N,N',N'-tetramethylenediamine, the mixture was stirred in deionized water at room temperature and 200-900 rpm for 0.1-5 hours. Then, a crosslinking reaction was carried out to obtain the sodium dodecylbenzenesulfonate hydrogel block.

[0037] According to some specific embodiments of the present invention, the sodium dodecylbenzenesulfonate hydrogel block is prepared by a method comprising the following steps:

[0038] Sodium dodecylbenzenesulfonate, acrylamide, and N,N'-methylenebisacrylamide were used as raw materials. In the presence of ammonium persulfate and N,N,N',N'-tetramethylenediamine, the mixture was stirred in deionized water at room temperature and 300-850 rpm for 0.3-4 hours. Then, a crosslinking reaction was carried out to obtain the sodium dodecylbenzenesulfonate hydrogel block.

[0039] According to some specific embodiments of the present invention, the sodium dodecylbenzenesulfonate hydrogel block is prepared by a method comprising the following steps:

[0040] Sodium dodecylbenzenesulfonate, acrylamide, and N,N'-methylenebisacrylamide were used as raw materials. In the presence of ammonium persulfate and N,N,N',N'-tetramethylenediamine, the mixture was stirred in deionized water at room temperature and 400-800 rpm for 0.8-3 hours. Then, a crosslinking reaction was carried out to obtain the sodium dodecylbenzenesulfonate hydrogel block.

[0041] According to some specific embodiments of the present invention, after the crosslinking reaction, the reaction further includes heating at 20-110°C for 8-30 hours to remove water from the reaction system, and then obtaining the sodium dodecylbenzenesulfonate hydrogel block.

[0042] According to some specific embodiments of the present invention, after the crosslinking reaction, the reaction system is further heated at 30-100°C for 15-28 hours to remove water.

[0043] According to some specific embodiments of the present invention, after the crosslinking reaction, the reaction system is further subjected to heating at 40-90°C for 16-26 hours to remove water.

[0044] According to some specific embodiments of the present invention, the step of applying a silica microsphere film to the surface of a material includes immersing the material in a dispersion system in which a silica microsphere film is formed on the surface, and then removing it, thereby applying the silica microsphere film to the surface of the material.

[0045] According to some specific embodiments of the present invention, the step of processing micro-nano structures on the surface of a material with a silica microsphere film using a laser includes first performing laser processing on the surface of the material with the silica microsphere film at a non-focal position of a laser lens to obtain nano-protrusions; and then performing laser processing at the focal position of the laser lens to obtain micron-grooves.

[0046] According to some specific embodiments of the present invention, the laser processing parameters in the step of obtaining nanoprotrusions by laser processing include:

[0047] The laser wavelength is 343nm, 515nm or 1030nm, and the focal length of the lens is 90-160mm;

[0048] The laser processing is performed with the laser defocused at a state of 0.2-3mm.

[0049] According to some specific embodiments of the present invention, the focal length of the lens in the step of laser processing to obtain the nano-protrusion is 95-150 mm.

[0050] According to some specific embodiments of the present invention, the focal length of the lens in the step of laser processing to obtain the nano-protrusion is 100-140 mm.

[0051] According to some specific embodiments of the present invention, in the step of laser processing to obtain nano-protrusions, the laser scanning speed is 1-9 mm / s, and the scanning trajectory spacing is 0.15-0.45 mm.

[0052] According to some specific embodiments of the present invention, the scanning trajectory spacing in the step of obtaining nanoprotrusions by laser processing is 0.18 to 0.42 mm.

[0053] According to some specific embodiments of the present invention, the scanning trajectory spacing in the step of laser processing to obtain nanoprotrusions is 0.21 to 0.40 mm.

[0054] According to some specific embodiments of the present invention, the scanning speed of the laser in the step of laser processing to obtain nanoprotrusions is 2 to 8 mm / s.

[0055] According to some specific embodiments of the present invention, the scanning speed of the laser in the step of laser processing to obtain nanoprotrusions is 3 to 6 mm / s.

[0056] According to some specific embodiments of the present invention, the repetition frequency of the laser in the step of laser processing to obtain nanoprotrusions is 1-200kHz.

[0057] According to some specific embodiments of the present invention, the repetition frequency of the laser in the step of laser processing to obtain nanoprotrusions is 100-150 kHz.

[0058] According to some specific embodiments of the present invention, the repetition frequency of the laser in the step of laser processing to obtain nanoprotrusions is 1-120kHz.

[0059] According to some specific embodiments of the present invention, the average power of the laser in the step of laser processing to obtain nanoprotrusions is 80-200mW.

[0060] According to some specific embodiments of the present invention, the average power of the laser in the step of laser processing to obtain nanoprotrusions is 90mW to 160mW.

[0061] According to some specific embodiments of the present invention, the average power of the laser in the step of laser processing to obtain nanoprotrusions is 95mW to 130mW.

[0062] According to some specific embodiments of the present invention, the laser processing parameters in the step of obtaining the micron-sized groove by laser processing include:

[0063] The laser wavelength is 343nm, 515nm or 1030nm, and the focal length of the lens is 90-160mm.

[0064] The scanning trajectory spacing for laser processing is 0.15-0.45 mm.

[0065] According to some specific embodiments of the present invention, the focal length of the lens in the step of laser processing to obtain the micron-groove is 95-150 mm.

[0066] According to some specific embodiments of the present invention, the focal length of the lens in the step of laser processing to obtain the micron-groove is 100-140 mm.

[0067] According to some specific embodiments of the present invention, the laser processing scanning trajectory spacing in the step of obtaining the micron-sized groove is 0.2 to 0.4 mm.

[0068] According to some specific embodiments of the present invention, the laser processing scanning trajectory spacing in the step of obtaining the micron-sized groove is 0.21 to 0.35 mm.

[0069] According to some specific embodiments of the present invention, in the step of laser processing to obtain the micron-sized groove, the laser scanning speed is 1-9 mm / s, and the processing is performed at the focal position under the lens.

[0070] According to some specific embodiments of the present invention, the scanning speed of the laser in the step of laser processing to obtain the micron-sized groove is 2 to 8 mm / s.

[0071] According to some specific embodiments of the present invention, the scanning speed of the laser in the step of laser processing to obtain the micron-sized groove is 2.5 to 7.5 mm / s.

[0072] According to some specific embodiments of the present invention, the repetition frequency of the laser in the step of laser processing to obtain the micron-sized groove is 1-200 kHz.

[0073] According to some specific embodiments of the present invention, the repetition frequency of the laser in the step of laser processing to obtain the micron-sized groove is 100 to 150 kHz.

[0074] According to some specific embodiments of the present invention, the repetition frequency of the laser in the step of laser processing to obtain the micron-sized groove is 1k to 120kHz.

[0075] According to some specific embodiments of the present invention, the average power of the laser in the step of laser processing to obtain the micron-sized groove is 0.5%-100% of the total laser energy of the system.

[0076] According to some specific embodiments of the present invention, in the step of laser processing to obtain nano-protrusions, the focal length of the lens is 95-150mm, and the processing is performed with a defocus of 0.5-2.5mm.

[0077] According to some specific embodiments of the present invention, in the step of laser processing to obtain nano-protrusions, the focal length of the lens is 100-140mm, and the processing is performed with a defocus of 0.75-2.05mm.

[0078] According to some specific embodiments of the present invention, the average laser power in the step of laser processing to obtain micron-sized grooves is 1W to 5W.

[0079] According to some specific embodiments of the present invention, the average laser power in the step of laser processing to obtain micron-sized grooves is 1.5W to 4.5W.

[0080] According to some specific embodiments of the present invention, the average laser power in the step of laser processing to obtain micron-sized grooves is 2.5W to 4.2W.

[0081] This invention processes materials under a femtosecond laser, and by adjusting the laser parameters, periodic nanoprotrusion structures are obtained on the material surface.

[0082] This invention places a material with periodic nano-protrusions at the focal position of a femtosecond laser and further processes it using straight lines in two parallel and perpendicular directions to prepare a micro-groove structure of a block array, ultimately obtaining a micro-nano structure surface in the shape of a micro cube.

[0083] According to some specific embodiments of the present invention, in the step of obtaining nanoprotrusions by laser processing, the laser processing path is a zigzag curve (e.g., Figure 7 As shown in A); the laser processing path in the step of obtaining micron-sized grooves through laser processing is grid-like (as shown in A). Figure 7 (As shown in B).

[0084] According to some specific embodiments of the present invention, the processing method further includes the steps of polishing and cleaning the material, and then depositing a silica microsphere film on the surface of the material; the polishing includes polishing the surface of the material to a Sa value of 0 to 0.1 μm; the cleaning includes cleaning the polished material surface in sequence with acetone, ethanol and water.

[0085] According to some specific embodiments of the present invention, the polishing of the material includes sanding with 100-10000 grit sandpaper and / or polishing with 1-30 nm polishing paste.

[0086] This invention obtains a material with low surface roughness and free of other impurities by polishing and cleaning the material.

[0087] According to some specific embodiments of the present invention, the processing method further includes a step of hydrophobically treating the surface of the material after processing the micro / nano structure, including hydrophobically treating the material surface with 1H,1H,2H,2H-perfluorooctyltriethoxysilane.

[0088] According to some specific embodiments of the present invention, the processing method further includes a step of hydrophobically treating the surface of the material after processing the micro-nano structure, which includes immersing the material after processing the micro-nano structure in an ethanol solution of 1H,1H,2H,2H-perfluorooctyltriethoxysilane and allowing it to stand, and then vacuum drying to obtain a hydrophobically modified material with a micro-nano structure surface.

[0089] According to some specific embodiments of the present invention, the mass concentration of 1H,1H,2H,2H-perfluorooctyltriethoxysilane in the ethanol solution of 1H,1H,2H,2H-perfluorooctyltriethoxysilane is 0.5%-15%.

[0090] According to some specific embodiments of the present invention, the mass concentration of 1H,1H,2H,2H-perfluorooctyltriethoxysilane in the ethanol solution of 1H,1H,2H,2H-perfluorooctyltriethoxysilane is 0.75-12%.

[0091] According to some specific embodiments of the present invention, the mass concentration of 1H,1H,2H,2H-perfluorooctyltriethoxysilane in the ethanol solution of 1H,1H,2H,2H-perfluorooctyltriethoxysilane is 1 to 10%.

[0092] According to some specific embodiments of the present invention, the material after processing the micro / nano structure is immersed in an ethanol solution of 1H,1H,2H,2H-perfluorooctyltriethoxysilane and left to stand for 1-80 min.

[0093] According to some specific embodiments of the present invention, the material after processing the micro-nano structure is immersed in an ethanol solution of 1H,1H,2H,2H-perfluorooctyltriethoxysilane and left to stand for 15 to 75 minutes.

[0094] According to some specific embodiments of the present invention, the material with the processed micro / nano structure is immersed in an ethanol solution of 1H,1H,2H,2H-perfluorooctyltriethoxysilane and left to stand for 30–65 min.

[0095] According to some specific embodiments of the present invention, vacuum drying is performed at 20-110°C for 5-50 minutes.

[0096] According to some specific embodiments of the present invention, the vacuum drying time is 10 to 35 minutes.

[0097] According to some specific embodiments of the present invention, the vacuum drying time is 15 to 30 minutes.

[0098] According to some specific embodiments of the present invention, the temperature of vacuum drying is 35–100°C.

[0099] According to some specific embodiments of the present invention, the temperature of vacuum drying is 55–95°C.

[0100] According to some specific embodiments of the present invention, the material is a metal.

[0101] According to some specific embodiments of the present invention, the material is steel.

[0102] According to some specific embodiments of the present invention, the material is bearing steel.

[0103] Furthermore, the present invention also provides materials with micro / nano structured surfaces obtained by the aforementioned processing method.

[0104] In summary, this invention provides a material with a micro / nano structured surface and a method for processing the same. The technical solution of this invention has the following advantages:

[0105] The bearing steel sheet with micro-nano structure obtained by the method of the present invention is impregnated in 1H,1H,2H,2H-perfluorooctyltriethoxysilane (FOTS) ethanol solution, so that the surface of the micro-cubic micro-nano structure combines with the chemical coating to have rose-shaped high adhesion superhydrophobic properties, and the structural properties enhance the mechanical wear resistance of the coating. Attached Figure Description

[0106] Figure 1 This is a flowchart of the method for preparing superhydrophobic micro / nano structures in Embodiment 1 of the present invention;

[0107] Figure 2 This is a schematic diagram of the self-assembly process of silica microspheres in Embodiment 1 of the present invention;

[0108] Figure 3 This is a SEM image of the silica microsphere monolayer film in Example 1 of the present invention;

[0109] Figure 4 An atomic force microscope image of the nanoprotrusions in Embodiment 1 of the present invention;

[0110] Figure 5 This is a three-dimensional optical profile characteristic image of the micrometer groove in Embodiment 1 of the present invention;

[0111] Figure 6 This is a schematic diagram of the wear test in Embodiment 1 of the present invention;

[0112] Figure 7 This is a comparison diagram of the contact angles of the micro-cubic micro / nano structure before and after wear in Embodiment 1 of the present invention;

[0113] Figure 8 This is a diagram showing the superhydrophobic contact angle of the micro / nano structure in Embodiment 1 of the present invention;

[0114] Figure 9 This is a laser scanning route diagram of the present invention. Detailed Implementation

[0115] The following detailed embodiments illustrate the implementation process and beneficial effects of the present invention, aiming to help readers better understand the essence and characteristics of the present invention, and are not intended to limit the scope of implementation of this case.

[0116] Example 1

[0117] according to Figure 1 The steps are as follows: use sandpaper of 200 to 4000 grit to polish the surface of the bearing steel plate (2cm×2cm×1mm), then use polishing paste with a particle size of 20 to 2nm to polish in sequence, and clean it with 15ml of acetone, ethanol and deionized water in sequence and then dry it for later use.

[0118] In this experiment, a 2.5 wt% 1 μm silica dispersion with a water-to-alcohol ratio of 3:7 was used and thoroughly dissolved by ultrasonication.

[0119] The preferred reagent ratio for preparing SDBS gel blocks is SDBS:MA:MBA:APS:TEMED:H2O = 1.4:2.1:0.03:0.015:0.008. Stir thoroughly at 650 rpm for 1 hour at room temperature. The hydrogel blocks are prepared by transferring them to a mold and heating at 30°C for 12 hours to complete cross-linking; after cross-linking, they are transferred to an oven and heated to 70°C for 24 hours to remove the added water. Using a 5 ml disposable dropper, two drops of silica dispersion with a particle size of 0.5–5 μm are added to a 75 ml culture dish containing water. The prepared SDBS gel block is then placed in the culture dish for 3 seconds and removed to complete the film preparation (e.g., ...). Figure 2 As shown in the figure, the SEM image of the obtained film is as follows. Figure 3 As shown.

[0120] The instrument used in this experiment was an ultrafast femtosecond laser with a wavelength of 515 nm, and the lens used had a focal length of 110 mm. Processing was performed with a defocus of 1.1 mm. The average laser power was 123 mW, and the repetition rate was set to 100 kHz. The laser scanning speed was set to 5 mm / s, and the spacing between continuous laser scanning trajectories was 0.25 mm. The laser was processed according to... Figure 9 The process follows a specific route to obtain a periodic nano-protrusion structure surface.

[0121] Meanwhile, the aforementioned periodic nano-protrusion structure is further processed using a straight line route in two parallel and perpendicular directions. Compared to the processing parameters of the nanostructure, the laser intensity is increased to 3.92W, and the process is carried out under a lens, ultimately resulting in a micro-nano structure bearing steel sheet with a micro-array.

[0122] Finally, the bearing steel sheet with the above micro-nano structure was placed in a 1.5% (w / w) 1H,1H,2H,2H-perfluorooctyltriethoxysilane (FOTS) ethanol solution and allowed to stand for 60 minutes, followed by vacuum drying at 70°C for 20 minutes.

[0123] like Figure 4 Figure 5 As shown, the micro / nanostructure dimensions of the obtained bearing steel surface are as follows: the spacing between nanoprotrusions is 1 μm, the height is 110 nm, the width of the microgrooves is 40 μm, the depth is 60 μm, and the distance between two adjacent microgrooves is 0.25 mm. The microgrooves form micro cubes of 0.25 mm × 0.25 mm, and each cube surface has approximately 62,500 nanoprotrusions.

[0124] Comparative Example 1

[0125] The surface of the bearing steel plate (2cm×2cm×1mm) was polished using sandpaper ranging from 200 to 4000 grit. Then, polishing was performed sequentially using polishing paste with a particle size of 20 to 2nm. The plate was then ultrasonically cleaned with a certain amount of acetone, ethanol, and deionized water, and dried for later use. Finally, it was immersed in a 1H,1H,2H,2H-perfluorooctyltriethoxysilane (FOTS) ethanol solution and allowed to stand. After vacuum drying, the hydrophobic modification was completed.

[0126] Test case

[0127] The bearing steel plate sample with hydrophobic coating micro / nano structure prepared in Example 1 was subjected to the following... Figure 6 The wear resistance test is shown. A 50g weight is placed on a 2×2cm bearing steel sample, and a wear cycle is completed by moving the weight horizontally by 20cm. This is repeated 10 times. Contact angle tests are performed before and after the test. This yields the bearing steel sample with nanostructures or microarrays prepared in Example 1 of this invention. The presence of nanostructures and microarrays improves the hydrophobicity of the sample and enhances the wear resistance of the chemical coating, respectively (e.g., ...). Figure 7 (As shown).

[0128] Compared to Comparative Example 1, the hydrophobic micro / nanostructure surface obtained using the above embodiments exhibits high adhesion, superhydrophobicity, and wear resistance (e.g., ...). Figure 7(As shown). By adjusting the solvent ratio of the silica dispersion, the pre-agglomeration of silica microspheres on the water surface was reduced, preventing the formation of a complete monolayer film. When the water-alcohol ratio was adjusted, pre-agglomeration was almost completely eliminated. Instead of relying on the surface tension gradient induced by the previous SDBS aqueous solution, the SDBS hydrogel block not only allows for repeated use but also improves experimental efficiency and simplifies experimental procedures (e.g., ...). Figure 2-3 (As shown). The dense silica film is crucial for the uniformity of subsequent laser nanofabrication. Compared to Comparative Example 1 and the nanostructured substrate surface alone, the contact angle decreased by approximately 7° after wear. When the laser processing trajectory spacing of the array micro / nano structure is 0.25 mm, the contact angle is 151.2° ± 0.9, decreasing by only about 4° after wear, and the micro / nano structure array surface achieves high adhesion and superhydrophobicity (e.g., ...). Figure 7 (As shown). When the substrate surface is rotated 90° or 180°, the 7ul water droplet still does not fall off (as shown). Figure 8 (As shown).

[0129] Specific examples have been used to illustrate the principles and implementation methods of this invention. The descriptions of the above embodiments are only for the purpose of helping to understand the method and core ideas of this invention. Furthermore, those skilled in the art will recognize that, based on the ideas of this invention, there will be changes in the specific implementation methods and application scope. Therefore, the content of this specification should not be construed as a limitation of this invention.

Claims

1. A method for processing the surface of a material micro / nano structure, the method comprising: The steps of depositing a silica microsphere film on the surface of the material and processing micro / nano structures on the surface of the material with the silica microsphere film deposited using a laser; The step of depositing a silica microsphere film on the surface of the material includes the following steps: preparing an alcohol-water dispersion of silica microspheres; adding the silica microsphere alcohol-water dispersion to water to obtain a dispersion system and adding sodium dodecylbenzenesulfonate hydrogel blocks to induce the liquid-gas interfacial tension gradient field of the system; obtaining a silica microsphere film through self-assembly of silica microspheres; and applying the silica microsphere film to the surface of the material. The volume ratio of water to alcohol in the alcohol-water dispersion is 1:9 to 1:1; Based on the total mass of the alcohol-water dispersion of the silica microspheres as 100%, the mass concentration of silica is 1.5~3.5 wt%. The silica microsphere alcohol aqueous dispersion is added to water at a ratio of dispersion to water of 1 / 1200 to 1 / 600. The material is a metal; The steps of processing micro- and nano-structures on the surface of a material with a silica microsphere film using a laser include first processing the surface of the material with the silica microsphere film at a non-focal position of a laser lens to obtain nano-protrusions; and then processing the surface at the focal position of the laser lens to obtain micro-grooves. The sodium dodecylbenzenesulfonate hydrogel block was prepared by a method comprising the following steps: Sodium dodecylbenzenesulfonate, acrylamide, and N,N'-methylenebisacrylamide were used as raw materials. A crosslinking reaction was carried out in deionized water in the presence of ammonium persulfate and N,N,N',N'-tetramethylenediamine to obtain the sodium dodecylbenzenesulfonate hydrogel block. The mass ratio of sodium dodecylbenzenesulfonate, acrylamide, N,N'-methylenebisacrylamide, ammonium persulfate, N,N,N',N'-tetramethylenediamine, and deionized water was (0.1-15):(0.1-20):(0.001-6):(0.001-3):(0.001-5):(1-30). The crosslinking reaction was carried out at 20-90℃ for 8-15 h.

2. The processing method according to claim 1, wherein, The volume ratio of water to alcohol in the alcohol-water dispersion is 1.5:8.5 to 4.5:5.

5.

3. The processing method according to claim 1, wherein, The volume ratio of water to alcohol in the alcohol-water dispersion is 2:8 to 4:

6.

4. The processing method according to claim 1, wherein, The silica is hydrophobic silica, and the contact angle of the hydrophobic silica is 120~140°.

5. The processing method according to claim 1, wherein, The mass ratio of sodium dodecylbenzenesulfonate, acrylamide, N,N'-methylenebisacrylamide, ammonium persulfate, N,N,N',N'-tetramethylenediamine and deionized water is (0.5-12):(0.5-16):(0.005-5):(0.005-2):(5-26):(0.002-4).

6. The processing method according to claim 1, wherein, The mass ratio of sodium dodecylbenzenesulfonate, acrylamide, N,N'-methylenebisacrylamide, ammonium persulfate, N,N,N',N'-tetramethylenediamine and deionized water is (1-9):(1-12):(0.012-3):(0.01-1.5):(0.003-3):(8-24).

7. The processing method according to claim 1, wherein, The sodium dodecylbenzenesulfonate hydrogel block was prepared by a method comprising the following steps: Sodium dodecylbenzenesulfonate, acrylamide, and N,N'-methylenebisacrylamide were used as raw materials. In the presence of ammonium persulfate and N,N,N',N'-tetramethylenediamine, the mixture was stirred in deionized water at room temperature and 200-900 rpm for 0.1-5 hours. Then, a crosslinking reaction was carried out to obtain the sodium dodecylbenzenesulfonate hydrogel block.

8. The processing method according to claim 1, wherein, After the crosslinking reaction, the reaction system is heated at 20-110°C for 8-30 hours to remove water, and then the sodium dodecylbenzenesulfonate hydrogel block is obtained.

9. The processing method according to any one of claims 1 to 8, wherein, The laser processing parameters in the step of obtaining nanoprotrusions by laser processing include: The laser wavelength is 343nm, 515nm or 1030nm, and the focal length of the lens is 90-160mm; The laser processing is performed with the laser defocused at a state of 0.2-3mm. The laser scanning speed is 1-9 mm / s, and the scanning trajectory spacing is 0.15-0.45 mm; The repetition frequency of the laser is 1-200kHz; The average power of the laser is 80-200mW; The laser processing parameters in the step of obtaining micron-sized grooves by laser processing include: The laser wavelength is 343nm, 515nm or 1030nm, and the focal length of the lens is 90-160mm. The scanning trajectory spacing for laser processing is 0.15-0.45 mm; The laser scanning speed is 1-9 mm / s, and the processing is performed at the focal point under the lens; The repetition frequency of the laser is 1-200kHz; The average power of the laser is 0.5%-100% of the total laser energy of the system.

10. The processing method according to claim 9, wherein, In the step of laser processing to obtain nano-protrusions, the laser processing path is a zigzag curve; in the step of laser processing to obtain micron-grooves, the laser processing path is a grid.

11. The processing method according to any one of claims 1 to 8, wherein, The processing method further includes polishing and cleaning the material, and then depositing a silica microsphere film on the surface of the material; the polishing includes polishing the surface of the material to a Sa value of 0~0.1μm; the cleaning includes cleaning the polished material surface in sequence with acetone, ethanol and water.

12. The processing method according to any one of claims 1 to 8, wherein, The processing method further includes a step of hydrophobically treating the surface of the material after processing the micro-nano structure, including using 1H,1H,2H,2H-perfluorooctyltriethoxysilane to hydrophobically treat the material surface.

13. The processing method according to claim 12, wherein, The steps of hydrophobically treating the surface of the material after processing micro-nano structures include immersing the material after processing micro-nano structures in an ethanol solution of 1H,1H,2H,2H-perfluorooctyltriethoxysilane and allowing it to stand, and then vacuum drying to obtain a hydrophobically modified material with a micro-nano structure surface.

14. The processing method according to claim 12, wherein, The mass concentration of 1H,1H,2H,2H-perfluorooctyltriethoxysilane in an ethanol solution is 0.5%-15%.

15. The processing method according to claim 12, wherein, The processed micro / nano structure material is immersed in an ethanol solution of 1H,1H,2H,2H-perfluorooctyltriethoxysilane and left to stand for 1-80 minutes.

16. The processing method according to claim 12, wherein, Vacuum drying is performed at 20-110℃ for 5-50 minutes.

17. The processing method according to any one of claims 1 to 8, wherein, The material is steel.

18. The processing method according to any one of claims 1 to 8, wherein, The material is bearing steel.

19. A material with a micro / nano structure surface obtained by the processing method according to any one of claims 1 to 18; wherein the micro / nano structure comprises nano-protrusions and micro-grooves disposed on the surface of the material, the height of the nano-protrusions being 20-120 nm, the bottom diameter being 500-1000 nm, the groove depth being 15-70 μm, and the groove width being 20-60 μm; the spacing between adjacent grooves being 0.1 mm to 3 mm, and the number of nano-protrusions in the grid formed by two sets of adjacent grooves being 30,000 to 400,000.

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