CN114290000A - Preparation method of self-cleaning super-hydrophobic micro-nano double microstructure on metal surface - Google Patents
Preparation method of self-cleaning super-hydrophobic micro-nano double microstructure on metal surface Download PDFInfo
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Abstract
The invention provides a preparation method of a self-cleaning super-hydrophobic micro-nano double microstructure of a metal surface, belonging to the technical field of surface modification of metal materials. The technical scheme is as follows: the method comprises the following steps: (1) carrying out sand blasting treatment on the surface of the magnesium alloy; (2) carrying out laser etching treatment; (3) and (4) anodizing. The invention has the beneficial effects that: the invention prepares a special structure with microscopic-scale concave-convex roughness and grooves mutually arranged on the surface of the magnesium alloy by a method of coupling a laser surface etching technology and anodic oxidation treatment. The magnesium alloy surface obtained by the composite preparation method has good super-hydrophobic capacity, low adhesion and self-cleaning capacity, and meanwhile, the corrosion resistance of the magnesium alloy surface is remarkably improved, and the application field of the magnesium alloy is expanded.
Description
Technical Field
The invention relates to the technical field of surface modification of metal materials, in particular to a preparation method of a self-cleaning super-hydrophobic micro-nano double microstructure on a metal surface.
Background
Among practical engineering materials, magnesium and magnesium alloys thereof have many advantages of small density, high specific stiffness and specific strength, good cutting performance, good casting performance, excellent shock absorption performance, good damping performance and the like, and are known as metal structure materials which have development and application potentials most in 21 st century green engineering. Magnesium is one of the elements which are most widely distributed in nature, and magnesium resources in China are very rich and are the first place in the world. The magnesium and the alloy thereof have wide application prospect in the fields of electronic equipment, biological application, automobile industry, aerospace and the like. However, magnesium alloys are very active in properties, have poor corrosion resistance, are easily reacted with other substances in the environment, and are very easily corroded particularly in the marine atmosphere and humid air, thus greatly limiting the wide application of the magnesium alloys in various fields. The prior research shows that the corrosion problem of the metal material can be effectively solved by proper surface modification treatment. The super-hydrophobic structure can effectively isolate the contact between the magnesium alloy matrix and a corrosive medium, and improve the wettability of the surface of the magnesium alloy, thereby greatly improving the corrosion resistance of the magnesium alloy. Therefore, the research on the surface of the super-hydrophobic structure of the magnesium alloy has very important significance for improving the corrosion resistance and expanding the application field.
In recent years, under the initiation of an interesting super-hydrophobic phenomenon on the surfaces of animals and plants in nature, more and more researchers at home and abroad are dedicated to the preparation and research of super-hydrophobic film layers on the surfaces of metal materials. The preparation of the superhydrophobic film layer is generally started from two aspects: firstly, a micro-rough structure is constructed on the surface of a metal material, the structure can trap a small amount of air in the structure, and the trapped air layer can effectively isolate a corrosive medium from contacting with a magnesium alloy matrix; secondly, the microstructure of the surface of the metal material is chemically modified by using a low-surface-energy substance to reduce the free energy of the surface of the metal material so as to prepare the super-hydrophobic structure surface. The super-hydrophobic surface prepared from the magnesium alloy can effectively prevent a corrosive medium and the wetting of the metal surface, greatly reduce the corrosion rate of the magnesium alloy surface and effectively improve the corrosion resistance of the magnesium alloy.
From the existing research situation, there are many methods for preparing the super-hydrophobic surface of the metal material at home and abroad, such as a sol-gel method, a template method, an electrostatic spinning method, an etching method, a vapor deposition method and the like. Recent research reports that Zhengshuli et al successfully prepares a super-hydrophobic coating with a contact angle of (155.2 +/-0.5) ° on the surface of aluminum by combining anodic oxidation and myristic acid modification, and the corrosion resistance of the aluminum-based super-hydrophobic coating is remarkably enhanced compared with that of an aluminum substrate (Zhengshuli et al, materials engineering, 2017,45(10): 71-78). The plum crystal and the like are subjected to brush plating treatment and laser micromachining coupled on an aluminum alloy substrate to obtain a special structure surface with grooves and convex hulls which are distributed together, the surface of a sample shows better stability at different temperatures, the contact angle is as high as 156 degrees, and the corrosion resistance is also obviously improved (the plum crystal and the like, Chinese mechanical engineering, 2017,28(1): 82-92). XuJi and the like successfully prepare a super-hydrophobic structure on the surface of the aluminum-magnesium alloy based on laser processing and self-assembly technology, the surface contact angle is as high as 156 degrees, and the super-hydrophobic effect is good (XuJi and the like, China non-ferrous metals academic report, 2012,22(7): 1855-1862). Shenzhou and the like successfully prepare a super-hydrophobic structure on the surface of a Ti6Al4V matrix by adopting a sand blasting-anodic oxidation method and FAS-17 modification, and the contact angle of the super-hydrophobic structure is as high as about 160 degrees, and the super-hydrophobic structure has higher stability. Chinese patent (202011274245.5) discloses a method for preparing a super-hydrophobic coating by chemically modifying with an ethanol solution of fluorosilane after a checkered structure is etched on the surface of a magnesium alloy through laser processing, so that the super-hydrophobic structure is successfully prepared on the surface of the magnesium alloy, the static contact angle is not less than 161 degrees, and the corrosion resistance is remarkably enhanced. Chinese patent (201010520898.7) discloses that a primary microstructure is firstly formed on the surface of magnesium alloy by adopting sulfuric acid etching treatment, and then a secondary structure and low surface energy modification are simultaneously carried out by an anodic oxidation method, so that a surface with low adhesion and good super-hydrophobic property is successfully obtained.
However, most of the above-mentioned preparation methods require complicated and expensive equipment, and the preparation cost is high, which is not suitable for large-scale production. Meanwhile, most reagents used in the preparation process are acid-base solutions harmful to the environment or toxic chemicals and the like. And the prepared super-hydrophobic surface has poor stability and is not wear-resistant, so that the obtained super-hydrophobic surface cannot meet the requirements of practical application.
How to solve the above technical problems is the subject of the present invention.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a preparation method of a metal surface self-cleaning super-hydrophobic micro-nano double microstructure, which has the advantages of simplicity, convenience, easiness, high stability of the metal surface micro-nano double microstructure and the like.
The invention idea of the invention is as follows: the invention provides a simple, convenient and feasible preparation method which is simple in equipment, low in preparation cost and harmless to the environment by preparing the super-hydrophobic micro-nano dual microstructure on the surface of the magnesium alloy through a method of sand blasting, laser etching, anodic oxidation and stearic acid modification treatment, and the prepared magnesium alloy surface has high-efficiency super-hydrophobic capability and good corrosion resistance.
In order to achieve the purpose, the invention adopts the following technical scheme: a preparation method of a self-cleaning super-hydrophobic micro-nano double microstructure of a metal surface comprises the following steps:
(1) AZ91 magnesium alloy was cut into 15mm × 25mm × 10mm samples, and 800 mm pieces were sequentially applied to the surface of the magnesium alloy#、1200#、2000#The sand paper is ground and polished, then the magnesium alloy which is ground and polished is sequentially ultrasonically cleaned and dried by acetone, ethanol and deionized water, and then pressure is usedCarrying out sand blasting treatment on the surface of the magnesium alloy by using micron-sized brown corundum sand pills through compressed air, wherein 36-180 meshes of brown corundum is used during sand blasting, the sand blasting pressure is 0.2-0.6 MPa, the distance between the sand blasting and the surface of the magnesium alloy sample is 15-25 cm, and the sand blasting time is 10 s-5 min;
(2) ultrasonically cleaning and drying a magnesium alloy sample subjected to sand blasting by using acetone, ethanol and deionized water in sequence, and performing gridding texture etching on the surface of the magnesium alloy, wherein the laser etching voltage is 15-20V, the current is 10-15A, the etching texture grid is 80-160 mu m, the focal length is 193mm, and the laser wavelength is 1064 nm;
(3) ultrasonically cleaning and blow-drying a magnesium alloy sample subjected to laser etching by using acetone, ethanol and deionized water in sequence, taking the obtained magnesium alloy sample as an anode, taking a platinum sheet as a cathode, wherein the distance between the anode and the cathode is 2cm, and performing anodic oxidation by using a sodium hydroxide solution as an electrolyte, wherein the concentration of the electrolyte is 0.1-0.5 mol/L, the anodic oxidation voltage is 4-12V, and the anodic oxidation time is 10-60 min;
(4) ultrasonically cleaning electrolyte remained on the surface of the magnesium alloy sample subjected to anodic oxidation treatment by using deionized water, drying the electrolyte, and then putting the electrolyte into an ethanol solution of stearic acid with the concentration of 0.025-0.15 mol/L for modification, wherein the modification time of the stearic acid is 4-40 h;
(5) taking out the modified magnesium alloy sample, washing the surface of the magnesium alloy sample by using an ethanol solution, putting the magnesium alloy sample into a constant-temperature drying oven, keeping the temperature for a proper time, taking out the magnesium alloy sample, wherein the temperature of the constant-temperature drying oven is 60-120 ℃, the keeping time is 20-40 min, and properly cooling the magnesium alloy sample in the air to obtain the superhydrophobic structure surface with low adhesion and corrosion resistance.
According to the further optimized scheme of the preparation method of the self-cleaning super-hydrophobic micro-nano double microstructure on the metal surface, the sand blasting process can change the surface appearance characteristics of the magnesium alloy substrate and construct a micron-sized concave-convex rough structure; the laser etching technology can etch and generate a micron-scale regular groove structure on the surface of the magnesium alloy.
According to the further optimized scheme of the preparation method of the self-cleaning super-hydrophobic micro-nano double microstructure on the metal surface, provided by the invention, the nano structure required for constructing the super-hydrophobic surface is generated on the surface of the magnesium alloy substrate by anodic oxidation treatment while the micro-scale rough structure generated by sand blasting treatment and laser etching is not influenced, so that a special structure with the mutual arrangement of micro-scale concave-convex roughness and grooves is formed.
As a further optimization scheme of the preparation method of the metal surface self-cleaning super-hydrophobic micro-nano double microstructure provided by the invention, stearic acid is a saturated long-chain fatty acid, consists of a linear long carbon chain and a carboxyl at one end, is weak in acidity, and generates Mg [ CH ] through self-assembly reaction between the carboxyl in stearic acid molecules and magnesium ions on the surface of a magnesium alloy during soaking modification3(CH2)16COO]2And the stearic acid is firmly combined on the surface of the magnesium alloy substrate, so that the hydrophobic long chain in the stearic acid is successfully grafted to the surface of the magnesium alloy with a micro-nano double microstructure through a chemical bond, and the surface free energy of the magnesium alloy is reduced.
According to a further optimized scheme of the preparation method of the metal surface self-cleaning super-hydrophobic micro-nano double microstructure provided by the invention, after the magnesium alloy is modified by stearic acid to reduce the surface free energy of the magnesium alloy, the micro-nano double microstructure on the surface of a sample can capture and seal enough air, and an 'air cushion' can be formed on the surface of the magnesium alloy, so that the contact between a corrosive medium and a magnesium alloy matrix can be effectively blocked, the actual solid-liquid contact area is obviously reduced, and the surface of the magnesium alloy can obtain better super-hydrophobic capacity and corrosion resistance.
Compared with the only polished magnesium alloy, the corrosion potential of the prepared magnesium alloy is improved by 0.222V, the corrosion current density is reduced by 2 orders of magnitude, the corrosion potential of the prepared magnesium alloy is-1.307V, and the corrosion current density is 3.165 multiplied by 10-6A/cm2And the capacitive reactance arc radius of the super-hydrophobic surface is far larger than that of the polished magnesium alloy.
As a further optimized scheme of the preparation method of the metal surface self-cleaning super-hydrophobic micro-nano dual microstructure provided by the invention, the prepared magnesium alloy has low adhesiveness, a surface contact angle of 159.8 degrees, good self-cleaning capability and remarkably enhanced corrosion resistance.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides a preparation method of a self-cleaning super-hydrophobic micro-nano double microstructure on a metal surface, wherein a method for producing a micron-sized coarse structure by combined processing of sand blasting and laser etching is high in surface structure stability and good in controllability in the preparation process.
2. According to the preparation method of the self-cleaning super-hydrophobic micro-nano double microstructure on the metal surface, provided by the invention, the micron-sized coarse structure generated by sand blasting and laser etching cannot be damaged by anodic oxidation treatment, and the nano composite structure required by the super-hydrophobic surface can be constructed, so that the reaction process is mild and the controllability is good.
3. According to the preparation method of the metal surface self-cleaning super-hydrophobic micro-nano double microstructure provided by the invention, the magnesium alloy surface prepared by the method of coupling physical etching and anodic oxidation has a special structure of micro-scale concave-convex roughness and grooves which are mutually arranged, the prepared magnesium alloy super-hydrophobic film layer is flat and moderate in thickness, has low adhesion and self-cleaning capability, the super-hydrophobic contact angle is more than 150 degrees, the corrosion resistance is remarkably improved, and the method is low in comprehensive cost and easy to industrially apply.
Drawings
Fig. 1 is an SEM topography of a micrometer-scale rough structure formed on a surface of a magnesium alloy after physical etching is performed on the surface by sand blasting in embodiment 1 of the present invention.
Fig. 2 is an SEM topography of a micrometer-scale regularly arranged groove structure formed on the surface of the magnesium alloy after the surface is subjected to laser etching treatment in embodiment 2 of the present invention.
FIG. 3 is an SEM topography of a microstructure formed on the surface of the magnesium alloy after the surface is anodized in example 2 of the present invention.
FIG. 4 is an X-ray diffraction chart of the surface of a magnesium alloy after the anodic oxidation treatment in example 3 of the present invention.
FIG. 5 is a graph of the electrochemical corrosion and AC impedance of the surface of the magnesium alloy in 3.5 wt.% NaCl solution in example 3.
FIG. 6 is a graph showing the surface adhesion of the magnesium alloy in example 3 of the present invention, which was measured by the pull-drop method.
Fig. 7 is a test chart of a self-cleaning experiment of the magnesium alloy super-hydrophobic surface in embodiment 3 of the present invention.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications or substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit and scope of the invention. The experimental methods and reagents of the formulations not specified in the examples are in accordance with the conventional conditions in the art.
Example 1
AZ91 magnesium alloy was cut into 15mm × 25mm × 10mm samples, and 800 mm pieces were sequentially applied to the surface of the magnesium alloy#，1200#，2000#And (3) grinding and polishing the sand paper, and then ultrasonically cleaning and drying the magnesium alloy subjected to grinding and polishing by using acetone, ethanol and deionized water in sequence.
And (3) carrying out sand blasting treatment on the surface of the magnesium alloy by using micron-sized brown corundum sand pills by using compressed air, wherein 80-mesh brown corundum is used during sand blasting, the sand blasting pressure is 0.5MPa, the distance between the sand blasting pills and the surface of the magnesium alloy sample is 20cm, and the sand blasting time is 30 s. And then ultrasonically cleaning the magnesium alloy sample with the rough structure surface by using acetone, ethanol and deionized water in sequence again and blow-drying. After the magnesium alloy surface is physically etched by sand blasting, the appearance of the micron-scale rough structure SEM formed on the surface is shown in figure 1.
And carrying out laser gridding texture etching on the surface of the magnesium alloy subjected to sand blasting, wherein the etching voltage is 17V, the current is 13A, the etching texture grid is 120 mu m, the focal length is 193mm, and the laser wavelength is 1064 nm. And then, ultrasonically cleaning the magnesium alloy sample subjected to the laser etching treatment by using acetone, ethanol and deionized water in sequence and blow-drying.
The magnesium alloy sample obtained by laser etching is used as an anode, a platinum sheet is used as a cathode, the distance between the anode and the cathode is 2cm, NaOH solution is used as electrolyte for anodic oxidation, the concentration of the electrolyte is 0.5mol/L, the anodic oxidation voltage is 6V, and the anodic oxidation time is 40 min. And then ultrasonically cleaning the electrolyte remained on the surface of the magnesium alloy sample subjected to the anodic oxidation treatment by using deionized water, and blow-drying the electrolyte.
And (3) putting the magnesium alloy sample subjected to the anodic oxidation treatment into an ethanol solution of stearic acid with the concentration of 0.075mol/L for modification, wherein the stearic acid modification time is 28 h. And then taking out the modified magnesium alloy sample, washing the surface of the magnesium alloy sample by using an ethanol solution, putting the magnesium alloy sample into a constant-temperature drying oven, keeping the temperature for a proper time, taking out the magnesium alloy sample, wherein the temperature of the constant-temperature drying oven is 80 ℃, the keeping time is 30min, and after the magnesium alloy sample is properly cooled in the air, the superhydrophobic structure surface with low adhesion and corrosion resistance can be obtained.
Example 2
AZ91 magnesium alloy was cut into 15mm × 25mm × 10mm samples, and 800 mm pieces were sequentially applied to the surface of the magnesium alloy#，1200#，2000#And (3) grinding and polishing the sand paper, and then ultrasonically cleaning and drying the magnesium alloy subjected to grinding and polishing by using acetone, ethanol and deionized water in sequence.
And (3) carrying out sand blasting treatment on the surface of the magnesium alloy by adopting the micron-sized brown corundum sand pills through compressed air, wherein 80-mesh brown corundum is used during sand blasting, the sand blasting pressure is 0.5MPa, the distance between the sand blasting pills and the surface of the magnesium alloy sample is 20cm, and the sand blasting time is 2 min. And then ultrasonically cleaning the magnesium alloy sample with the rough structure surface by using acetone, ethanol and deionized water in sequence again and blow-drying.
And carrying out laser gridding texture etching on the surface of the magnesium alloy subjected to sand blasting, wherein the etching voltage is 16V, the current is 13.8A, the etching texture grid is 80 mu m, the focal length is 193mm, and the laser wavelength is 1064 nm. And then, ultrasonically cleaning the magnesium alloy sample subjected to the laser etching treatment by using acetone, ethanol and deionized water in sequence and blow-drying. After the surface of the magnesium alloy is subjected to laser etching treatment, the surface of the magnesium alloy is provided with micron-scale regularly-arranged groove structures, and the SEM appearance is shown in FIG. 2.
The magnesium alloy sample obtained by laser etching is used as an anode, a platinum sheet is used as a cathode, the distance between the anode and the cathode is 2cm, NaOH solution is used as electrolyte for anodic oxidation, the concentration of the electrolyte is 0.4mol/L, the anodic oxidation voltage is 10V, and the anodic oxidation time is 30 min. And then ultrasonically cleaning the electrolyte remained on the surface of the magnesium alloy sample subjected to the anodic oxidation treatment by using deionized water, and blow-drying the electrolyte. After the surface of the magnesium alloy is subjected to anodic oxidation treatment, the microstructure SEM appearance formed on the surface is shown in FIG. 3.
And (3) putting the magnesium alloy sample subjected to the anodic oxidation treatment into an ethanol solution of stearic acid with the concentration of 0.025mol/L for modification, wherein the stearic acid modification time is 20 h. And then taking out the modified magnesium alloy sample, washing the surface of the magnesium alloy sample by using an ethanol solution, putting the magnesium alloy sample into a constant-temperature drying oven, keeping the temperature for a proper time, taking out the magnesium alloy sample, wherein the temperature of the constant-temperature drying oven is 100 ℃, the keeping time is 20min, and after the magnesium alloy sample is properly cooled in the air, the superhydrophobic structure surface with low adhesion and corrosion resistance can be obtained.
Example 3
AZ91 magnesium alloy was cut into 15mm × 25mm × 10mm samples, and 800 mm pieces were sequentially applied to the surface of the magnesium alloy#，1200#，2000#And (3) grinding and polishing the sand paper, and then ultrasonically cleaning and drying the magnesium alloy subjected to grinding and polishing by using acetone, ethanol and deionized water in sequence.
And (3) carrying out sand blasting treatment on the surface of the magnesium alloy by using micron-sized brown corundum sand pills by using compressed air, wherein 80-mesh brown corundum is used during sand blasting, the sand blasting pressure is 0.5MPa, the distance between the sand blasting pills and the surface of the magnesium alloy sample is 20cm, and the sand blasting time is 30 s. And then ultrasonically cleaning the magnesium alloy sample with the rough structure surface by using acetone, ethanol and deionized water in sequence again and blow-drying.
And carrying out laser gridding texture etching on the surface of the magnesium alloy subjected to sand blasting, wherein the etching voltage is 16V, the current is 13.8A, the etching texture grid is 80 mu m, the focal length is 193mm, and the laser wavelength is 1064 nm. And then, ultrasonically cleaning the magnesium alloy sample subjected to the laser etching treatment by using acetone, ethanol and deionized water in sequence and blow-drying.
The magnesium alloy sample obtained by laser etching is used as an anode, a platinum sheet is used as a cathode, the distance between the anode and the cathode is 2cm, NaOH solution is used as electrolyte for anodic oxidation, the concentration of the electrolyte is 0.4mol/L, the anodic oxidation voltage is 10V, and the anodic oxidation time is 30 min. And then ultrasonically cleaning the electrolyte remained on the surface of the magnesium alloy sample subjected to the anodic oxidation treatment by using deionized water, and blow-drying the electrolyte.
And (3) putting the magnesium alloy sample subjected to the anodic oxidation treatment into an ethanol solution of stearic acid with the concentration of 0.05mol/L for modification, wherein the stearic acid modification time is 24 h. And then taking out the modified magnesium alloy sample, washing the surface of the magnesium alloy sample by using an ethanol solution, putting the magnesium alloy sample into a constant-temperature drying oven, keeping the temperature for a proper time, taking out the magnesium alloy sample, wherein the temperature of the constant-temperature drying oven is 80 ℃, the keeping time is 30min, and after the magnesium alloy sample is properly cooled in the air, the superhydrophobic structure surface with low adhesion and corrosion resistance can be obtained. The X-ray diffraction pattern of the surface of the magnesium alloy after the anodic oxidation treatment is shown in FIG. 4. The electrochemical corrosion curve and the alternating current impedance diagram of the magnesium alloy surface in a 3.5 wt.% NaCl aqueous solution shown in FIG. 5 show that, through tests, compared with a magnesium alloy sample which is only polished, the corrosion potential of the super-hydrophobic magnesium alloy is increased by 0.222V, the corrosion current density is reduced by 2 orders of magnitude, and the capacitive arc radius of the super-hydrophobic surface is far larger than that of the polished magnesium alloy, so that the magnesium alloy surface shows good corrosion resistance. The graph of the surface adhesion of the magnesium alloy in this example, which is shown in fig. 6 and tested by the pull-up water drop method, shows that water drops can be easily removed from the surface, showing a good hydrophobic effect. The test shows that the magnesium alloy super-hydrophobic surface has a static contact angle of 159.8 degrees to water drops. The test chart of the magnesium alloy super-hydrophobic surface self-cleaning experiment is shown in fig. 7, which shows that water drops are easy to fall from the surface of the super-hydrophobic structure, and surface pollutants on a rolling path are also taken away by the water drops, so that the self-cleaning capability is good.
Example 4
AZ91 magnesium alloy was cut into 15mm by 25mm by 10mm samplesSequentially using 800 on the surface of the magnesium alloy#，1200#，2000#And (3) grinding and polishing the sand paper, and then ultrasonically cleaning and drying the magnesium alloy subjected to grinding and polishing by using acetone, ethanol and deionized water in sequence.
And (3) carrying out sand blasting treatment on the surface of the magnesium alloy by adopting the micron-sized brown corundum sand pills through compressed air, wherein 80-mesh brown corundum is used during sand blasting, the sand blasting pressure is 0.5MPa, the distance between the sand blasting pills and the surface of the magnesium alloy sample is 20cm, and the sand blasting time is 5 min. And then ultrasonically cleaning the magnesium alloy sample with the rough structure surface by using acetone, ethanol and deionized water in sequence again and blow-drying.
And carrying out laser gridding texture etching on the surface of the magnesium alloy subjected to sand blasting, wherein the etching voltage is 18V, the current is 14A, the etching texture grid is 140 micrometers, the focal length is 193mm, and the laser wavelength is 1064 nm. And then, ultrasonically cleaning the magnesium alloy sample subjected to the laser etching treatment by using acetone, ethanol and deionized water in sequence and blow-drying.
The magnesium alloy sample obtained by laser etching is used as an anode, a platinum sheet is used as a cathode, the distance between the anode and the cathode is 2cm, NaOH solution is used as electrolyte for anodic oxidation, the concentration of the electrolyte is 0.4mol/L, the anodic oxidation voltage is 10V, and the anodic oxidation time is 30 min. And then ultrasonically cleaning the electrolyte remained on the surface of the magnesium alloy sample subjected to the anodic oxidation treatment by using deionized water, and blow-drying the electrolyte.
And (3) putting the magnesium alloy sample subjected to the anodic oxidation treatment into an ethanol solution of stearic acid with the concentration of 0.1mol/L for modification, wherein the stearic acid modification time is 32 h. And then taking out the modified magnesium alloy sample, washing the surface of the magnesium alloy sample by using an ethanol solution, putting the magnesium alloy sample into a constant-temperature drying oven, keeping the temperature for a proper time, taking out the magnesium alloy sample, wherein the temperature of the constant-temperature drying oven is 100 ℃, the keeping time is 30min, and after the magnesium alloy sample is properly cooled in the air, the superhydrophobic structure surface with low adhesion and corrosion resistance can be obtained.
The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the invention, and any local variations in the formulation and process thereof should be considered within the scope of the present invention.
Claims (7)
1. A preparation method of a self-cleaning super-hydrophobic micro-nano double microstructure on a metal surface is characterized by comprising the following steps:
(1) sequentially using the magnesium alloy surface 800#、1200#、2000#The abrasive paper is ground and polished, the polished magnesium alloy is sequentially ultrasonically cleaned and dried by acetone, ethanol and deionized water, and then the surface of the magnesium alloy is subjected to sand blasting treatment by using a micron-sized brown-corundum sand pill by using compressed air to construct a micron-sized concave-convex rough structure on the surface of the magnesium alloy;
(2) ultrasonically cleaning and drying the magnesium alloy sample subjected to sand blasting by using acetone, ethanol and deionized water in sequence, carrying out laser texture processing on the surface of the sample, selecting etched textures as grids, and constructing a groove structure with micron-scale regular arrangement on the surface of the magnesium alloy;
(3) ultrasonically cleaning and blow-drying a magnesium alloy sample subjected to laser etching treatment by using acetone, ethanol and deionized water in sequence, and carrying out anodic oxidation treatment by using the obtained magnesium alloy sample as an anode, a platinum sheet as a cathode and a sodium hydroxide solution as an electrolyte to construct a nano structure required by the superhydrophobic surface of the magnesium alloy;
(4) ultrasonically cleaning electrolyte remained on the surface of the magnesium alloy sample subjected to anodic oxidation treatment by using deionized water, blow-drying the electrolyte, and then putting the electrolyte into an ethanol solution of stearic acid for modification;
(5) and taking out the modified magnesium alloy sample, washing the surface of the magnesium alloy sample by using an ethanol solution, putting the magnesium alloy sample into a constant-temperature drying oven, preserving the heat for a period of time, taking out the magnesium alloy sample, and cooling to obtain the superhydrophobic structure surface with low adhesion and corrosion resistance.
2. The preparation method of the metal surface self-cleaning super-hydrophobic micro-nano dual microstructure according to claim 1, wherein in the step (1), the magnesium alloy is cut into samples with the size of 15mm × 25mm × 10mm, brown corundum with 36-180 meshes is used during sand blasting, the sand blasting pressure is 0.2-0.6 MPa, the distance between the magnesium alloy sample and the surface during sand blasting is 15-25 cm, and the sand blasting time is 10 s-5 min.
3. The preparation method of the metal surface self-cleaning super-hydrophobic micro-nano dual microstructure according to claim 1, wherein the laser etching voltage in the step (2) is 15-20V, the current is 10-15A, the etching texture grid is 80-160 μm, the focal length is 193mm, and the laser wavelength is 1064 nm.
4. The method for preparing the metal surface self-cleaning super-hydrophobic micro-nano dual microstructure according to claim 1, wherein the distance between the anode and the cathode is 2cm during the anodic oxidation treatment in the step (3), a sodium hydroxide solution is used as an electrolyte for anodic oxidation, the concentration of the electrolyte is 0.1-0.5 mol/L, the anodic oxidation voltage is 4-12V, and the anodic oxidation time is 10-60 min.
5. The preparation method of the metal surface self-cleaning super-hydrophobic micro-nano dual microstructure according to claim 1, wherein the concentration of the stearic acid ethanol solution in the step (4) is 0.025-0.15 mol/L, and the modification time of stearic acid is 4-40 h.
6. The preparation method of the metal surface self-cleaning super-hydrophobic micro-nano dual microstructure according to claim 1, wherein the temperature in the constant-temperature drying oven in the step (5) is 60-120 ℃, the heat preservation time is 20-40 min, and air cooling is performed after drying.
7. The method for preparing the self-cleaning super-hydrophobic micro-nano dual microstructure on the metal surface according to any one of claims 1 to 6, wherein a special dual-microstructure structure with roughness and grooves mutually arranged is constructed on the surface of the magnesium alloy by a method of coupling a laser processing surface etching technology and anodic oxidation treatment, and then the special dual-microstructure structure is modified by an ethanol solution of stearic acid.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114836802A (en) * | 2022-04-21 | 2022-08-02 | 长春理工大学 | Adhesive composite processing method of micro-nano hydrophobic structure |
| CN114850785A (en) * | 2022-04-14 | 2022-08-05 | 哈尔滨工业大学 | Method for preparing super-hydrophobic coating by utilizing reaction wetting |
| CN115029767A (en) * | 2022-05-31 | 2022-09-09 | 珠海市湖大科技有限公司 | Preparation method of inorganic super-hydrophobic surface of aluminum alloy |
| CN115161733A (en) * | 2022-09-08 | 2022-10-11 | 苏州优缘建材有限公司 | Surface treatment structure of aluminum alloy and preparation method thereof |
| CN115418641A (en) * | 2022-09-08 | 2022-12-02 | 南通大学 | Preparation method of super-hydrophobic anticorrosive surface of metal material |
| CN116479368A (en) * | 2023-04-18 | 2023-07-25 | 宝鸡市永盛泰钛业有限公司 | Corrosion-resistant high-strength titanium alloy and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101476142A (en) * | 2008-12-24 | 2009-07-08 | 华南理工大学 | Preparation of metallic surface super-hydrophobic organic nano film |
| CN104561999A (en) * | 2014-12-19 | 2015-04-29 | 北京科技大学 | Method for preparing superhydrophobic film on magnesium alloy surface |
| KR20150078976A (en) * | 2013-12-31 | 2015-07-08 | 한국전기연구원 | Molds fabricated using lithography and anodizing and superhydrophobic materials fabricated using the mold |
| CN105689237A (en) * | 2016-04-11 | 2016-06-22 | 四川大学 | Manufacturing method for super-hydrophobic metal surface |
| CN107723773A (en) * | 2017-08-22 | 2018-02-23 | 吉林大学 | A kind of preparation method on the bionical anti-icing surface of aluminium alloy |
| CN112358812A (en) * | 2020-11-15 | 2021-02-12 | 吉林大学 | Magnesium alloy super-hydrophobic coating and preparation method and application thereof |
| CN113249726A (en) * | 2021-05-10 | 2021-08-13 | 中国石油大学(华东) | Method for preparing micron-sized spherical super-hydrophobic composite coating on surface of magnesium alloy |
-
2021
- 2021-12-30 CN CN202111650394.1A patent/CN114290000A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101476142A (en) * | 2008-12-24 | 2009-07-08 | 华南理工大学 | Preparation of metallic surface super-hydrophobic organic nano film |
| KR20150078976A (en) * | 2013-12-31 | 2015-07-08 | 한국전기연구원 | Molds fabricated using lithography and anodizing and superhydrophobic materials fabricated using the mold |
| CN104561999A (en) * | 2014-12-19 | 2015-04-29 | 北京科技大学 | Method for preparing superhydrophobic film on magnesium alloy surface |
| CN105689237A (en) * | 2016-04-11 | 2016-06-22 | 四川大学 | Manufacturing method for super-hydrophobic metal surface |
| CN107723773A (en) * | 2017-08-22 | 2018-02-23 | 吉林大学 | A kind of preparation method on the bionical anti-icing surface of aluminium alloy |
| CN112358812A (en) * | 2020-11-15 | 2021-02-12 | 吉林大学 | Magnesium alloy super-hydrophobic coating and preparation method and application thereof |
| CN113249726A (en) * | 2021-05-10 | 2021-08-13 | 中国石油大学(华东) | Method for preparing micron-sized spherical super-hydrophobic composite coating on surface of magnesium alloy |
Non-Patent Citations (1)
| Title |
|---|
| 周荃卉: "喷砂-阳极氧化-氟化处理构筑铝合金超疏水表面", 高等学校化学学报, vol. 31, no. 3, 10 March 2010 (2010-03-10), pages 456 - 462 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114850785A (en) * | 2022-04-14 | 2022-08-05 | 哈尔滨工业大学 | Method for preparing super-hydrophobic coating by utilizing reaction wetting |
| CN114836802A (en) * | 2022-04-21 | 2022-08-02 | 长春理工大学 | Adhesive composite processing method of micro-nano hydrophobic structure |
| CN115029767A (en) * | 2022-05-31 | 2022-09-09 | 珠海市湖大科技有限公司 | Preparation method of inorganic super-hydrophobic surface of aluminum alloy |
| CN115029767B (en) * | 2022-05-31 | 2023-12-29 | 湖北大学 | Preparation method of inorganic superhydrophobic surface of aluminum alloy |
| CN115161733A (en) * | 2022-09-08 | 2022-10-11 | 苏州优缘建材有限公司 | Surface treatment structure of aluminum alloy and preparation method thereof |
| CN115418641A (en) * | 2022-09-08 | 2022-12-02 | 南通大学 | Preparation method of super-hydrophobic anticorrosive surface of metal material |
| CN115161733B (en) * | 2022-09-08 | 2022-12-13 | 苏州优缘建材有限公司 | Surface treatment structure of aluminum alloy and preparation method thereof |
| CN116479368A (en) * | 2023-04-18 | 2023-07-25 | 宝鸡市永盛泰钛业有限公司 | Corrosion-resistant high-strength titanium alloy and preparation method thereof |
| CN116479368B (en) * | 2023-04-18 | 2023-09-29 | 宝鸡市永盛泰钛业有限公司 | Corrosion-resistant high-strength titanium alloy and preparation method thereof |
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