CN115922092A - Ant-crypt-shaped super-hydrophobic surface and preparation method thereof - Google Patents
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Abstract
The invention relates to the technical field of laser processing, and particularly provides an ant-cave-shaped superhydrophobic surface and a preparation method thereof, wherein a micron groove is processed on the surface of an aluminum alloy by ultrafast laser, amorphous silicon oxide is doped into the micron groove under the action of the ultrafast laser, and the micron groove is melted and decomposed by instantaneous high temperature and high pressure generated by the ultrafast laser to form the ant-cave-shaped superhydrophobic surface which is beneficial to existence and maintenance of a material surface gas layer; a large number of nano particles are accumulated near the cave mouth, and the channel of the ant cave-shaped superhydrophobic surface is bent and extended from top to bottom, so that an air layer in the ant cave-shaped superhydrophobic surface can be effectively locked, water drops are prevented from entering the ant cave-shaped superhydrophobic surface, the superhydrophobic performance of the material surface is greatly improved, and meanwhile, the superhydrophobic surface is made of a metal material, so that the superhydrophobic surface has a high-stability superhydrophobic 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-cave-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 concerned by people. Generally, the preparation process of the super-hydrophobic material is to realize the super-hydrophobic property by preparing a micro-nano structure on the surface of the material and coating organic chemical substances with low surface energy. Although significant research progress has been made in the preparation of superhydrophobic materials, the surface of the superhydrophobic material generally has the defects of low mechanical strength, poor chemical stability and the like, so that the superhydrophobic material still faces a plurality of important challenges in practical application.
In fact, the non-wetting and repelling effect of the surface of the super-hydrophobic material on the contact liquid is largely due to the existence of the air layer inside the micro-nano structure, but the air bags are often unstable in practical application environments, for example, when the material is in an environment of seawater soaking, steam condensation, ultraviolet irradiation and the like, the volume of the air bags is easy to reduce or even disappear, and finally the surface is changed from the Cassie-Baxter state to the Wenzel state.
Researchers have further enhanced the damage-proof capability of air cushions by changing the surface structure topography in response to this problem. Domingues et al, compare the stability of simple cylindrical, single concave cavity and double concave cavity structures in a wet environment. The results show that the breakthrough pressure of water on the simple cylindrical structure is 0kPa, while the breakthrough pressure on the surface of the biconcave cavity structure is typically greater than 100kPa. In addition, the air layer in the biconcave cavity structure shows better stability, and is prolonged by more than 7 orders of magnitude compared with a simple cylindrical structure. The multilayer biconcave cavity microstructure prepared by Sun et al provides multiple energy barriers for liquid intrusion, so that the maximum breakthrough pressure is increased by 2~3 times than that of a single-layer concave cavity structure. However, the existing method for enhancing the surface thermodynamic stability by designing the structure has the problems that the preparation process is complex, the low-surface-energy coating needs to be modified, the surface air cushion is difficult to repair after being damaged, and the like. In addition, the super-hydrophobic surface is always exposed to various external forces such as friction, stretching, bending and scouring impact of rainwater in real environment, so that the surface structure is abraded, cracked, flattened and peeled, and the liquid repellency of the surface is lost. Researchers have improved the mechanical durability of surfaces by designing more complex structures. For example, researchers have designed armor superhydrophobic surfaces, and through cyclic wear experiments, the mechanical durability of the surfaces can be prolonged by 10 times compared with that of traditional superhydrophobic surfaces, but low-surface-energy organic substances are still required for modifying the surfaces to achieve superhydrophobic performance. The Chinese patent with the publication date of 26/3/2022 and the application number of 202210308182.3 discloses a metal-based nest type microstructure superhydrophobic surface and a preparation method thereof. Obviously, the method is based on the electrochemical principle essentially, not only the process is complex, but also the size of the obtained nest type structure is in the micron order, and the nano-scale preparation is difficult to obtain; in addition, the nest structure has certain similarity with ant nests only at the surface openings, and does not prepare a complex fine structure which is more beneficial to improving the super-hydrophobic durability in the nest.
Therefore, a super-hydrophobic surface with simple preparation process, strong corrosion resistance and good hydrophobic effect and a preparation method thereof are needed.
Disclosure of Invention
The invention aims to solve the problems and provides an ant-cave-shaped super-hydrophobic surface and a preparation method thereof.
The ant-cave-shaped super-hydrophobic surface provided by the invention adopts a metal surface, a micron groove is formed on the metal surface, a plurality of ant cave piles are distributed on the metal surface and the micron groove, the ant cave piles form a periodic micron structure, each ant cave pile comprises a cave mouth and a channel which is bent and extended from top to bottom, a plurality of nano particles are distributed at the position close to the cave mouth, air bags are formed among the nano particles, and the channels are formed by curved surfaces with different curvatures.
Preferably, the depth of the micron groove is 60 to 80 μm.
Preferably, the opening size of the hole is 100 to 500nm.
Preferably, the size of the nanoparticles is 10 to 30nm.
Preferably, the ant-crypt superhydrophobic surface is inherently hydrophobic.
Preferably, the micro-grooves are periodically distributed.
A method for preparing an ant-pocket-shaped super-hydrophobic surface comprises the following steps:
s1, processing a first micrometer groove with micrometer magnitude on the metal surface by adopting ultrafast laser, wherein the pulse width of the ultrafast laser is 30fs to 300ps, the laser power is 400mw to 900mw, the scanning speed is 0.1mm/S to 5mm/S, and the scanning distance is 30 mu m to 100 mu m;
s2, placing the light-transmitting substance containing the dopant on the first micron groove, irradiating the light-transmitting substance containing the dopant by using ultrafast laser, doping the dopant into the first micron groove, and melting and decomposing the first micron groove by using instantaneous heat and pressure generated by the ultrafast laser to form the ant-cave-shaped superhydrophobic surface.
Preferably, the depth of the first micron groove is 30 to 60 μm.
Preferably, in S2, the ultrafast laser acts on a contact interface between the light-transmitting substance containing the dopant and the metal surface, the ultrafast laser deepens the first micrometer groove to form a second micrometer groove, and the depth of the second micrometer groove is 60 to 80 μm.
Preferably, the metal surface is made of aluminum alloy, titanium alloy or stainless steel.
Preferably, the light-transmitting substance containing the dopant is inorganic glass, organic glass or calcium fluoride crystal.
Compared with the prior art, the invention can obtain the following beneficial effects:
the super-hydrophobic surface is a bionic ant-cave micro-nano structure, has space complexity, simultaneously has extremely small cave mouth of the ant-cave structure, and is accumulated with a large number of nano particles nearby, the ant-cave structure can effectively lock an air layer therein, prevents water drops from entering, and greatly improves the super-hydrophobic performance of the surface of the material.
The super-hydrophobic surface of the invention adopts a metal material, and not only has a high stable super-hydrophobic effect, but also has an excellent anti-corrosion effect.
The ant hole design of the invention can be applied to the fields of corrosion resistance and super hydrophobicity, self-cleaning, pollution prevention, icing resistance and the like.
Drawings
FIG. 1 is a microstructure diagram of a first micro-groove provided in accordance with an embodiment of the present invention;
fig. 2 is a topographical view of an ant nest-like superhydrophobic surface provided in accordance with an embodiment of the present invention;
fig. 3 is a flow chart of a method for preparing an ant-crypt superhydrophobic surface provided in accordance with an embodiment of the present invention;
fig. 4 is a comparative graph of superhydrophobic permanence performance characterization of ant crypt-shaped superhydrophobic surfaces provided in accordance with an embodiment of the invention.
Wherein the reference numerals include:
the contact angle and rolling angle measurement curve 1 of the ant-shaped super-hydrophobic surface and the contact angle and rolling angle measurement curve 2 of the conventional micron groove structure surface.
Detailed Description
Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the following description, the same reference numerals are used for the same blocks. In the case of the same reference numerals, their names and functions are also the same. Therefore, 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 described in further detail below with reference to the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not to be construed as limiting the invention.
Fig. 1 illustrates a microstructure of a first micro-trench provided in accordance with an embodiment of the present invention.
As shown in fig. 1, the ant-pocket-shaped superhydrophobic surface provided in the embodiment of the present invention is made of an aluminum alloy material, and may also be made of other metal materials capable of generating an ant pocket structure, where the aluminum alloy surface is provided with micron grooves shown in fig. 1, and the micron grooves are distributed in a periodic manner, that is, the micron grooves.
Fig. 2 shows a local topography of an ant nest superhydrophobic surface provided according to an embodiment of the invention.
As shown in fig. 2 (a), a large number of ant colony piles are distributed on the surface of the aluminum alloy and in the micro grooves, the surface of the aluminum alloy refers to the upper surface of a protrusion formed by the adjacent micro grooves, the micro grooves refer to the side walls and the bottom of the grooves, the appearance of the ant colony piles is complex and is a periodic micro structure, and the length of the ant colony piles is usually 10 to 100 μm.
As shown in fig. 2 (b), the surface of the ant pocket pile has pockets, and the opening size of the pockets is usually 100 to 500nm. In addition, a large number of nanoparticles are densely distributed near the opening of the cavity.
As shown in fig. 2 (c), the size of the nanoparticles is usually 10 to 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 profile of the ant pocket stack, and fig. 2 (e) shows a partially enlarged profile of the cross-section of the ant pocket stack, and it can be seen that the channels inside the ant pocket stack are in an intricate and complex state extending from top to bottom in a curved manner, and the channels are composed of surfaces with various curvatures, thereby helping to firmly lock the air layer therein, so that the ant pocket-shaped superhydrophobic surface can be maintained for a long time even in a seawater immersion environment.
As shown in fig. 2 (f), the second micrometer groove depth is 60 to 80 μm.
To verify the effectiveness of the preparation method of ant crypt-shaped superhydrophobic surfaces, three examples are given below:
example one
Fig. 3 shows a flow of a method for preparing an ant nest-shaped superhydrophobic surface according to an embodiment of the present invention.
As shown in fig. 3, the method for preparing an ant-crypt-shaped superhydrophobic surface according to an embodiment of the present invention includes the following steps:
s1, polishing the surface of 6061 aluminum alloy by using sand paper, ultrasonically cleaning the surface of 6061 aluminum alloy by using deionized water, drying by using nitrogen, and ensuring that the surface to be processed is clean and dry, wherein other cleaning methods can be adopted.
S2, placing the cleaned 6061 aluminum alloy on a precise three-dimensional moving platform, and ablating the surface of the material by gathering ultrafast laser to form a first micron-sized groove with the depth of 30 microns, wherein 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 microns.
And S3, placing a piece of light-transmitting substance containing dopant on the surface of the first micron groove formed by processing in the S2, wherein in the embodiment, a fused silica glass sheet containing amorphous silicon oxide is adopted, ultrafast laser with the same parameters as those in the S2 is irradiated on a contact interface of the fused silica glass sheet and 6061 aluminum alloy, under the action of the laser, the silicon oxide is doped into the first micron groove, the first micron groove is melted and decomposed by instantaneous high temperature and high pressure generated by the ultrafast laser to form an ant cave structure extending from top to bottom, the first micron groove is deepened by the ultrafast laser to form a second micron groove, and the depth of the second micron groove is deepened to be 60 micrometers.
And S4, ultrasonically cleaning the surface of the 6061 aluminum alloy obtained in the S3 for 30 minutes by using deionized water again, and then carrying out low-temperature annealing treatment on the surface of the material to reduce the surface energy of the material, thereby finishing the preparation of the ant-cave-shaped super-hydrophobic surface. The hydrophobic performance test is carried out on the ant-shaped cave-shaped super-hydrophobic surface, and the contact angle of the ant-shaped cave-shaped super-hydrophobic surface to a water drop is 154 degrees.
As a preferred example, the metal for preparing the ant-colony-shaped superhydrophobic surface is not limited to the aluminum alloy, but includes other metal materials capable of producing an ant-colony structure.
As a preferred embodiment, the dopant used in the laser processing is not limited to silicon oxide, but other substances containing oxygen, or other substances that can form amorphous alloys or metal compounds with the metal elements in the metal surface can be used. When the metal surface is made of aluminum alloy, the dopant has the main function of reacting oxygen with aluminum in the aluminum alloy to generate metal oxide, and the metal oxide forms an amorphous state under the action of laser so as to enhance the hardness and the superhydrophobic effect of the ant-cave-shaped superhydrophobic surface. The light-transmitting substance is only used as a carrier of the dopant in the laser irradiation process, and the light-transmitting substance needs to ensure a good light-transmitting effect. The light-transmitting substance containing dopant can be inorganic glass, organic glass or calcium fluoride crystal.
Fig. 4 shows a superhydrophobic lasting performance characterization curve of an ant nest-like superhydrophobic surface provided according to an embodiment of the invention.
In order to verify the effectiveness of the ant-cave-shaped super-hydrophobic surface and the preparation method provided by the embodiment of the invention, the ant-cave-shaped super-hydrophobic surface is prepared according to the preparation method, and a verification comparison test is carried out on the ant-cave-shaped super-hydrophobic surface and the surface of the conventional micron groove structure, the ant-cave-shaped super-hydrophobic surface and the surface of the conventional micron groove structure are soaked in a sodium chloride (NaCl) solution with the concentration of 3.5% for simulating the soaking condition in seawater, the change condition of the contact angle and the rolling angle of the surface along with the soaking time is measured, and a contact angle and rolling angle measuring curve 1 of the ant-cave-shaped super-hydrophobic surface and a contact angle and rolling angle measuring curve 2 of the surface of the conventional micron groove structure are drawn, and as shown in a figure 4, the result is that the ant-cave-shaped super-hydrophobic surface is soaked in a simulated seawater solution for 100 days, the change of the contact angle and the rolling angle are smaller, the ant-cave-shaped super-hydrophobic surface still has obvious hydrophobicity, but the surface of the conventional micron groove structure is changed into hydrophilicity after being soaked in the simulated seawater for one week, and the hydrophobic performance of the conventional micron groove structure is destroyed.
Experiments show that the prepared ant-cave-shaped super-hydrophobic surface not only has a high-stability super-hydrophobic effect, but also has an excellent anti-corrosion effect.
The ant hole design of the invention can be applied to the fields of corrosion resistance and super-hydrophobicity, and can also be applied to the fields of self-cleaning, pollution prevention, icing resistance and the like.
Example two
The preparation of ant-cryptic superhydrophobic surfaces was performed according to the procedure of example one, except that:
the depth of the first micron groove in the S2 is 60 mu m, the pulse width of the ultrafast laser is 300ps, the laser power is 900mw, the scanning speed is 5mm/S, and the scanning distance is 100 mu m.
The depth of the second micron groove in S3 deepens to 80 μm.
The ant-crypt-shaped superhydrophobic surface obtained in this example had a contact angle to a water droplet of 151 °. The curve of the results of the comparative test for the validation using the ant-crypt-shaped superhydrophobic surface is substantially the same as that of the first example.
EXAMPLE III
The preparation of ant-cryptic superhydrophobic surfaces was performed according to the procedure of example one, except that:
the depth of the first micron groove in S2 is 50 μm, the pulse width of ultrafast laser is 40fs, the laser power is 600mw, the scanning speed is 1mm/S, and the scanning distance is 60 μm.
The depth of the second micro groove in S3 deepens to 70 μm.
The contact angle of the ant-crypt-shaped superhydrophobic surface obtained in this example to a water droplet was 158 °. The curve of the results of the comparative test for the validation using the ant-crypt-shaped superhydrophobic surface is substantially the same as that of the first example.
While embodiments of the present invention have been shown and described above, it should be understood that the above embodiments are exemplary and should not be taken as limiting the invention. Variations, modifications, substitutions and alterations of the above-described embodiments may be made by those of ordinary skill in the art without departing from the scope of the present invention.
The above embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.
Claims (11)
1. The ant cave-shaped super-hydrophobic surface is characterized in that a metal surface is adopted, a micron groove is formed in the metal surface, a plurality of ant cave piles are distributed on the metal surface and the micron groove, the ant cave piles form a periodic micron structure, each ant cave pile comprises a cave opening and a channel which extends in a bending mode from top to bottom, a plurality of nano particles are distributed at the position, close to the cave opening, of the cave opening, air bags are formed among the nano particles, and the channels are formed by curved surfaces with different curvatures.
2. The ant-pocket superhydrophobic surface of claim 1, wherein the micro-grooves have a depth of 60 to 80 μm.
3. The ant-pocketed superhydrophobic surface of claim 1, wherein an opening size of the pocket is 100 to 500nm.
4. The ant-pocketed superhydrophobic surface of claim 1, wherein the nanoparticles have a size of 10 to 30nm.
5. The ant-pocketed superhydrophobic surface of claim 1, wherein the ant-pocketed superhydrophobic surface is intrinsically superhydrophobic.
6. The ant-pocket superhydrophobic surface of claim 1, wherein the micro-grooves are periodically distributed.
7. A method for preparing an ant-pocket-shaped super-hydrophobic surface is characterized by comprising the following steps:
s1, processing a first micrometer groove with micrometer magnitude on the metal surface by adopting an ultrafast laser, wherein the pulse width of the ultrafast laser is 30fs to 300ps, the laser power is 400mw to 900mw, the scanning speed is 0.1mm/S to 5mm/S, and the scanning distance is 30 micrometers to 100 micrometers;
s2, placing a light-transmitting substance containing a dopant on the first micron groove, irradiating the light-transmitting substance containing the dopant by using the ultrafast laser, doping the dopant into the first micron groove, and melting and decomposing the first micron groove by using heat and pressure generated by the ultrafast laser to form the ant-cave-shaped superhydrophobic surface.
8. The method for preparing an ant-crypt-shaped superhydrophobic surface according to claim 7, wherein the depth of the first micro groove is 30 to 60 μm.
9. The method for preparing the ant-crypt-shaped superhydrophobic surface of claim 7, wherein in S2, the ultrafast laser acts on a contact interface between a light-transmitting substance containing a dopant and a metal surface, the ultrafast laser deepens the first micrometer groove to form a second micrometer groove, and the depth of the second micrometer groove is 60 to 80 micrometers.
10. The method of making an ant nest-shaped superhydrophobic surface of claim 7, wherein the metal surface is aluminum alloy, titanium alloy, stainless steel.
11. The method for producing an ant-crypt-shaped superhydrophobic surface according to claim 7, wherein the light-transmitting substance containing a dopant is inorganic glass, organic glass or calcium fluoride crystal.
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