CN115922092B - Ant cave-shaped super-hydrophobic surface and preparation method thereof - Google Patents
Ant cave-shaped super-hydrophobic surface and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of laser processing, in particular to an ant cavity-shaped super-hydrophobic surface and a preparation method thereof, wherein micron grooves are processed on the surface of an aluminum alloy mainly through ultrafast laser, amorphous silicon oxide is doped into the micron grooves under the action of the ultrafast laser, and the micron grooves are melted and decomposed by utilizing instantaneous high temperature and high pressure generated by the ultrafast laser to form the ant cavity-shaped super-hydrophobic surface which is favorable for the existence and maintenance of a material surface air layer; a large number of nano particles are accumulated near the hole mouth, and the channels of the ant hole-shaped super-hydrophobic surface are bent and extended from top to bottom, so that an air layer in the material can be effectively locked, water drops are prevented from entering the material, the super-hydrophobic performance of the material surface is greatly improved, and meanwhile, the super-hydrophobic surface is made of a metal material, so that the material has a high stable super-hydrophobic effect and an excellent anti-corrosion effect.
Description
Technical Field
The invention relates to the technical field of laser processing, and particularly provides an ant cavity-shaped super-hydrophobic surface and a preparation method thereof.
Background
The surface of the super-hydrophobic material has the functions of self-cleaning, corrosion resistance, drag reduction and the like, so that the super-hydrophobic material is widely focused by people. In general, the preparation process of the super-hydrophobic material is to prepare a micro-nano structure on the surface of the material and coat low-surface energy organic chemical substances to realize the super-hydrophobic performance. Although important research progress has been made in the preparation of super-hydrophobic materials at present, the surface of the super-hydrophobic materials has the defects of low mechanical strength, poor chemical stability and the like, so that the super-hydrophobic materials still face a plurality of important challenges in practical application.
In fact, the non-wetting and repulsive effects of the surface of the superhydrophobic material on the contact liquid are due to the existence of an air layer inside the micro-nano structure to a large extent, but these air bags are often unstable in practical application environments, for example, when the material is subjected to seawater immersion, steam condensation, ultraviolet irradiation and the like, the air bag volume is easily reduced or even eliminated, and finally the surface is changed from the Cassie-Baxter state to the Wenzel state.
Researchers have further enhanced the anti-vandalism capability of the cushion by altering the topography of the surface structure to address this problem. Dominages et al compared the stability of simple cylindrical, single-cavity and double-cavity structures in a wet environment. The results show that the breakthrough pressure of water on a simple cylindrical structure is 0kPa, while the breakthrough pressure on the surface of a biconcave cavity structure is typically greater than 100kPa. In addition, the air layer in the biconcave cavity structure exhibits better stability, prolonged by more than 7 orders of magnitude compared with a simple cylindrical structure. The multi-layer double-concave cavity microstructure prepared by Sun et al provides multiple energy barriers for the intrusion of liquid, so that the maximum breakthrough pressure is improved by 2-3 times compared with the single-layer concave cavity microstructure. However, the existing method for enhancing the thermodynamic stability of the surface by designing the structure has the problems that the preparation process is complex, the low-surface-energy coating is inevitably required to be modified, the surface air cushion is difficult to repair after being damaged, and the like. In addition, the superhydrophobic surface is always exposed to various external forces such as friction, stretching, bending, scouring impact of rainwater and the like in a real environment, so that the surface structure is worn, broken, flattened and peeled off, and the surface loses liquid repellency. Researchers have increased the mechanical durability of surfaces by designing more complex structures. For example, researchers designed armor superhydrophobic surfaces, and cyclic wear experiments found that the mechanical durability of the surface can be prolonged by 10 times compared with that of a traditional superhydrophobic surface, but low surface energy organics are still required to modify the surface in order to achieve superhydrophobic performance. Chinese patent publication No. 202210308182.3, 2022, 3 and 26 discloses a metal-based nest type microstructure superhydrophobic surface and a preparation method thereof, wherein a sample is immersed in a special solution and subjected to an electrifying reaction to prepare a nest structure, and then the nest structure is immersed in a myristic acid solution and subjected to an electrifying reaction to reduce the surface energy, so that the metal-based nest type microstructure superhydrophobic surface is obtained. Obviously, the method is based on an electrochemical principle, the process is complex, the size of the nest structure is also in the micrometer level, and the nanometer level preparation is difficult to obtain; in addition, the nest structure has certain similarity with the ant nest only at the surface opening, and a complex microstructure which is more beneficial to improving the super-hydrophobic durability is not prepared inside the nest.
Therefore, there is a need for a superhydrophobic surface with simple preparation process, strong corrosion resistance and good hydrophobic effect and a preparation method thereof.
Disclosure of Invention
The invention aims to solve the problems, and provides an ant-cavity-shaped super-hydrophobic surface and a preparation method thereof.
The ant cavity-shaped super-hydrophobic surface provided by the invention adopts a metal surface, micron grooves are formed in the metal surface, a plurality of ant cavity piles are distributed on the metal surface and the micron grooves, the ant cavity piles form a periodic micron structure, each ant cavity pile comprises a cavity opening and a channel which is bent and extended from top to bottom, a plurality of nano particles are distributed at the adjacent position of the cavity opening, air bags are formed among the nano particles, and the channel is formed by curved surfaces with different curvatures.
Preferably, the depth of the micro-grooves is 60-80 μm.
Preferably, the opening size of the hole is 100-500 nm.
Preferably, the size of the nano particles is 10-30 nm.
Preferably, the ant-cavity superhydrophobic surface is intrinsically hydrophobic.
Preferably, the micro grooves are periodically distributed.
The preparation method of the ant cavity-shaped super-hydrophobic surface comprises the following steps:
s1, processing a first micron groove with a micron level on the surface of a metal by using ultra-fast laser, wherein the pulse width of the ultra-fast laser is 30 fs-300 ps, the laser power is 400-900 mw, the scanning speed is 0.1-5 mm/S, and the scanning interval is 30-100 mu m;
s2, placing the light-transmitting substance containing the dopant on the first micro groove, irradiating the light-transmitting substance containing the dopant by using ultra-fast laser, doping the dopant into the first micro groove, and melting and decomposing the first micro groove by using instantaneous heat and pressure generated by the ultra-fast laser to form the ant-cavity-shaped super-hydrophobic surface.
Preferably, the depth of the first micro-groove is 30-60 μm.
Preferably, in S2, the ultrafast laser acts on the contact interface between the dopant-containing light-transmitting material and the metal surface, and the ultrafast laser deepens the first micro-groove to form a second micro-groove, where the depth of the second micro-groove is 60-80 μm.
Preferably, the metal surface is made of aluminum alloy, titanium alloy or stainless steel.
Preferably, the dopant-containing light-transmitting substance is an inorganic glass, an organic glass or calcium fluoride crystal.
Compared with the prior art, the invention has the following beneficial effects:
the super-hydrophobic surface of the invention is a bionic ant cavity micro-nano structure, which has space complexity, meanwhile, the cavity mouth of the ant cavity structure is extremely small, and a large number of nano particles are accumulated nearby the ant cavity structure, so that the ant cavity structure can effectively lock an air layer in the ant cavity structure, prevent water drops from entering, and greatly improve the super-hydrophobic performance of the material surface.
The super-hydrophobic surface of the invention adopts metal materials, thus not only having high stable super-hydrophobic effect, but also having excellent anti-corrosion effect.
The ant cavity design of the invention can be applied not only to the fields of corrosion resistance and superhydrophobicity, but also to the fields of self-cleaning, pollution prevention, ice coating resistance and the like.
Drawings
FIG. 1 is a microstructure view of a first micro-trench provided in accordance with an embodiment of the present invention;
fig. 2 is a partial topography of an ant-cavity superhydrophobic surface provided according to an embodiment of the invention;
fig. 3 is a flowchart of a method for preparing an ant cavity-shaped superhydrophobic surface according to an embodiment of the invention;
fig. 4 is a graph showing comparison of super-hydrophobic durability characteristics of ant cryptate super-hydrophobic surfaces provided according to an embodiment of the present invention.
Wherein reference numerals include:
the contact angle and rolling angle of the ant cavity-shaped super-hydrophobic surface are measured according to a curve 1 and the contact angle and rolling angle of the conventional micro-groove structure surface are measured according to a curve 2.
Detailed Description
Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. In the following description, like modules are denoted by like reference numerals. In the case of the same reference numerals, their names and functions are also the same. Therefore, a detailed description thereof will not be repeated.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not to be construed as limiting the invention.
Fig. 1 shows the microstructure of a first micro-groove provided according to an embodiment of the present invention.
As shown in fig. 1, the ant cavity-shaped superhydrophobic surface provided by the embodiment of the invention adopts an aluminum alloy material, and other metal materials capable of generating an ant cavity structure can be adopted, and the aluminum alloy surface is provided with the micrometer grooves shown in fig. 1, wherein the micrometer grooves are distributed in a periodic manner, namely, the micrometer grooves.
Fig. 2 shows a partial morphology of an ant-cavity superhydrophobic surface provided according to an embodiment of the invention.
As shown in fig. 2 (a), a plurality of ant hole piles are distributed on the surface of the aluminum alloy and in the micro grooves, the surface of the aluminum alloy is the upper surface of the protrusions formed by the adjacent micro grooves, the micro grooves are the side walls and the bottom of the grooves, the ant hole piles are complex in shape and are of periodic micro structures, and the length of the ant hole piles is 10-100 μm in general.
As shown in fig. 2 (b), the surface of the ant nest stack has a nest opening, and the opening size of the nest opening is typically between 100 to 500nm. In addition, a large number of nanoparticles are densely distributed near the openings.
As shown in fig. 2 (c), in general, the size of the nanoparticles is between 10 and 30nm, and fine air pockets can be formed between the nanoparticles, and the air pockets can effectively prevent water drops from entering.
Fig. 2 (d) shows the overall cross-sectional morphology of the ant hole pile, fig. 2 (e) shows the enlarged partial morphology of the cross-section of the ant hole pile, and it can be seen that the channels inside the ant hole pile are in a state of being intricate and bent and extended from top to bottom, and the channels are composed of a plurality of different curvature surfaces, so that the air layers in the channels are firmly locked, and the ant hole-shaped super-hydrophobic surfaces can be permanently maintained even in a seawater soaking environment.
As shown in fig. 2 (f), the second micro groove depth is 60 to 80 μm.
To verify the effectiveness of the preparation method of the ant cryptate superhydrophobic surface, the following three examples are given:
example 1
Fig. 3 shows a flow of a preparation method of an ant cavity-shaped superhydrophobic surface according to an embodiment of the invention.
As shown in fig. 3, the preparation method of the ant cavity-shaped superhydrophobic surface provided by the embodiment of the invention comprises the following steps:
s1, polishing the 6061 aluminum alloy surface by using sand paper, ultrasonically cleaning the 6061 aluminum alloy surface by using deionized water, and drying by using nitrogen to ensure that the surface to be processed is clean and dry, and other cleaning methods can be adopted.
S2, placing the 6061 aluminum alloy after cleaning on a precise three-dimensional moving platform, and forming a micron-sized first micron groove on the surface of the material by means of ablation of concentrated ultrafast laser, wherein the depth of the first micron groove is 30 mu m, the pulse width of the ultrafast laser is 30fs, the laser power is 400mw, the scanning speed is 0.1mm/S, and the scanning interval is 30 mu m.
S3, placing a piece of light-transmitting substance containing dopants on the surface of the first micro-groove formed by processing in S2, in the embodiment, adopting a fused quartz glass sheet containing amorphous silicon oxide, irradiating ultra-fast laser with the same parameters as those in S2 on a contact interface between the fused quartz glass sheet and 6061 aluminum alloy, doping the silicon oxide into the first micro-groove under the action of the laser, melting and decomposing the first micro-groove by instantaneous high temperature and high pressure generated by the ultra-fast laser to form an ant cavity structure extending from top to bottom, and deepening the first micro-groove by the ultra-fast laser to form a second micro-groove, wherein the depth of the second micro-groove is deepened to 60 mu m.
And S4, ultrasonically cleaning the 6061 aluminum alloy surface obtained in the step S3 for 30 minutes by adopting deionized water again, and then carrying out low-temperature annealing treatment on the aluminum alloy surface to reduce the surface energy of the material, thereby completing the preparation of the ant cavity-shaped super-hydrophobic surface. And carrying out a hydrophobic performance test on the ant cavity-shaped super-hydrophobic surface, wherein the contact angle of the ant cavity-shaped super-hydrophobic surface to water drops is 154 degrees.
As a preferred example, the metal for preparing the ant cavity-like superhydrophobic surface is not limited to aluminum alloy, but includes other metal materials capable of producing an ant cavity structure.
As a preferred example, the dopant in the laser processing is not limited to silicon oxide, but may be other substances containing oxygen element, or other substances that can form amorphous alloy or metal compound with the metal element in the metal surface. When the aluminum alloy is adopted on the metal surface, the main function of the dopant is to react oxygen element with aluminum in the aluminum alloy to generate metal oxide, and the metal oxide forms an amorphous state under the action of laser, so that the hardness and the superhydrophobic effect of the ant cavity superhydrophobic surface are enhanced. The light-transmitting substance is only used as a carrier of the dopant in the laser irradiation process, and a good light-transmitting effect needs to be ensured. The light-transmitting substance containing the dopant can be specifically inorganic glass, organic glass, calcium fluoride crystal or the like.
Fig. 4 shows a superhydrophobic durability characterization curve of an ant-cavity superhydrophobic surface provided according to an embodiment of the invention.
In order to verify the effectiveness of the ant cavity-shaped superhydrophobic surface and the preparation method provided by the embodiment of the invention, the ant cavity-shaped superhydrophobic surface is prepared and obtained according to the preparation method, and is subjected to a verification comparison test, the ant cavity-shaped superhydrophobic surface and the conventional micro groove structure surface are soaked in sodium chloride (NaCl) solution with the concentration of 3.5%, so that the soaking condition in seawater is simulated, the change condition of the surface contact angle and the rolling angle along with the soaking time is measured, the contact angle and the rolling angle measuring curve 1 of the ant cavity-shaped superhydrophobic surface and the contact angle and the rolling angle measuring curve 2 of the conventional micro groove structure surface are drawn, the result is shown as a figure 4, the ant cavity-shaped superhydrophobic surface is soaked in the simulated seawater for 100 days, the contact angle and the rolling angle change amount are small, the surface of the conventional micro groove structure surface is converted into hydrophilicity after being soaked in the simulated seawater for one week, and the hydrophobic property is destroyed.
Experiments prove that the prepared ant cavity-shaped super-hydrophobic surface not only has a high stable super-hydrophobic effect, but also has an excellent anti-corrosion effect.
The ant cavity design of the invention can be applied not only to the fields of corrosion resistance and superhydrophobicity, but also to the fields of self-cleaning, pollution prevention, ice coating resistance and the like.
Example two
The preparation of the ant-cavity superhydrophobic surface was performed according to the procedure of example one, except that:
the depth of the first micrometer groove in the S2 is 60 micrometers, the pulse width of the ultrafast laser is 300ps, the laser power is 900mw, the scanning speed is 5mm/S, and the scanning interval is 100 micrometers.
The depth of the second micro-groove in S3 deepens to 80 μm.
The contact angle of the ant cavity-like superhydrophobic surface obtained in this example to a water drop was 151 °. The result curve of the verification comparative test using the ant-cavity superhydrophobic surface is substantially identical to the result curve of the first embodiment.
Example III
The preparation of the ant-cavity superhydrophobic surface was performed according to the procedure of example one, except that:
the depth of the first micrometer groove in S2 is 50 micrometers, the pulse width of the ultrafast laser is 40fs, the laser power is 600mw, the scanning speed is 1mm/S, and the scanning interval is 60 micrometers.
The depth of the second micro-groove in S3 deepens to 70 μm.
The contact angle of the ant cavity-like superhydrophobic surface obtained in this example to a water drop was 158 °. The result curve of the verification comparative test using the ant-cavity superhydrophobic surface is substantially identical to the result curve of the first embodiment.
While embodiments of the present invention have been illustrated and described above, it will be appreciated that the above described embodiments are illustrative and should not be construed as limiting the invention. Variations, modifications, alternatives and variations of the above-described embodiments may be made by those of ordinary skill in the art within the scope of the present invention.
The above embodiments of the present invention do not limit the scope of the present invention. Any other corresponding changes and modifications made in accordance with the technical idea of the present invention shall be included in the scope of the claims of the present invention.
Claims (8)
1. The ant cavity-shaped super-hydrophobic surface is characterized in that a metal surface is adopted, micron grooves are formed in the metal surface, a plurality of ant cavity piles are distributed on the metal surface and the micron grooves, the ant cavity piles form a periodic micron structure, each ant cavity pile comprises a cavity opening and a channel which is bent and extends from top to bottom, a plurality of nano particles are distributed at the adjacent position of the cavity opening, air bags are formed among the nano particles, and the channel is formed by curved surfaces with different curvatures;
the depth of the micro groove is 60-80 mu m;
the opening size of the hole is 100-500 nm;
the size of the nano particles is 10-30 nm.
2. The ant-cavity superhydrophobic surface of claim 1, wherein the ant-cavity superhydrophobic surface is intrinsically superhydrophobic.
3. The ant-cavity superhydrophobic surface of claim 1, wherein the micro grooves are periodically distributed.
4. A method for preparing the ant-cavity-shaped superhydrophobic surface according to claim 1, comprising the steps of:
s1, processing a first micron groove with a micron level on a metal surface by using ultra-fast laser, wherein the pulse width of the ultra-fast laser is 30 fs-300 ps, the laser power is 400-900 mw, the scanning speed is 0.1-5 mm/S, and the scanning interval is 30-100 mu m;
s2, placing a light-transmitting substance containing a dopant on the first micro-groove, irradiating the light-transmitting substance containing the dopant by using the ultrafast laser, doping the dopant into the first micro-groove, and melting and decomposing the first micro-groove by using heat and pressure generated by the ultrafast laser to form an ant cavity-shaped superhydrophobic surface; the dopant is a substance containing oxygen element or other substances which can form amorphous alloy or metal compound with the metal element in the metal surface.
5. The method for preparing an ant-cavity-shaped superhydrophobic surface according to claim 4, wherein the depth of the first micro groove is 30-60 μm.
6. The method according to claim 4, wherein in S2, the ultrafast laser acts on a contact interface between the dopant-containing transparent substance and the metal surface, and the ultrafast laser deepens the first micro grooves to form second micro grooves, wherein the depth of the second micro grooves is 60-80 μm.
7. The method for preparing an ant-cavity superhydrophobic surface according to claim 4, wherein the metal surface is made of aluminum alloy, titanium alloy or stainless steel.
8. The method for preparing an ant-cavity superhydrophobic surface according to claim 4, wherein the dopant-containing light-transmitting substance is inorganic glass, organic glass or calcium fluoride crystal.
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| WO2008091242A2 (en) * | 2005-12-21 | 2008-07-31 | Uva Patent Foundation | Systems and methods of laser texturing and crystallization of material surfaces |
| US20150136226A1 (en) * | 2006-09-29 | 2015-05-21 | University Of Rochester | Super-hydrophobic surfaces and methods for producing super-hydrophobic surfaces |
| CN101219506B (en) * | 2008-01-07 | 2010-06-02 | 江苏大学 | Laser production method for metal base ultra-hydrophobicity micro-structure surface |
| DE102011121546B4 (en) * | 2011-12-20 | 2013-07-11 | Eads Deutschland Gmbh | Method for structuring a surface of a workpiece |
| US20180066131A1 (en) * | 2016-09-05 | 2018-03-08 | NanoSD Inc. | Polymer nanoparticle thermal insulators |
| EP3535214A1 (en) * | 2016-11-06 | 2019-09-11 | William Marsh Rice University | Methods of fabricating laser-induced graphene and compositions thereof |
| KR102308050B1 (en) * | 2020-04-10 | 2021-10-01 | 울산대학교 산학협력단 | Superhydrophobic surface making method and Superhydrophobic substrate repairing method same using |
| CN115193666A (en) * | 2022-05-20 | 2022-10-18 | 大连海事大学 | Preparation method of super-hydrophobic surface with micro-nano scale step structure for anti-icing |
| CN115717231B (en) * | 2023-01-09 | 2023-05-12 | 中国科学院长春光学精密机械与物理研究所 | Paracrystalline metal material, preparation method and application thereof |
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