CN109023319B - Method for preparing copper oxide super-hydrophobic coating with dendritic micro-nano structure - Google Patents
Method for preparing copper oxide super-hydrophobic coating with dendritic micro-nano structure Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1689—After-treatment
- C23C18/1692—Heat-treatment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1837—Multistep pretreatment
- C23C18/1844—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
Abstract
The invention discloses a method for simply and quickly preparing a copper oxide super-hydrophobic coating with a dendritic micro-nano structure. Firstly, preparing copper oxide with a dendritic micron structure through chemical replacement and direct thermal oxidation processes; the chemical replacement liquid can be copper chloride aqueous solution, and can also be mixed aqueous solution of copper sulfate and ferric chloride (or sodium chloride); immersing the processed matrix sample into a chemical displacement solution to form a non-smooth copper deposition layer on the surface of the sample; placing the copper deposit layer in a muffle furnace, carrying out heat treatment for a certain time, and directly thermally oxidizing the copper deposit layer into copper oxide to obtain copper oxide with a dendritic micro-nano structure; and finally, obtaining the super-hydrophobic copper oxide coating through low-energy modification. The static contact angle of the deionized water and the copper oxide super-hydrophobic coating is more than 150 degrees, and the rolling angle is less than 10 degrees. The copper oxide super-hydrophobic coating prepared by the method does not need complex and expensive equipment, has simple process and strong repeatability, can be applied to the surfaces of aluminum, magnesium, zinc, iron and the like, and is suitable for industrial production.
Description
Technical Field
The invention relates to the field of surface modification of metal materials, in particular to a method for preparing a copper oxide super-hydrophobic coating with a dendritic micro-nano structure. The service life of the aluminum material is prolonged by the inherent hydrophobic, anti-corrosion, anti-scaling and self-cleaning functions of the super-hydrophobic surface.
Background
For nearly thirty years, special wettability film layers, especially super-hydrophobic film layers, have become a research hotspot in the fields of domestic and foreign micro-nano materials and surface science. The inherent functions of water resistance, stain resistance, corrosion resistance, frost resistance and the like of the super-hydrophobic coating effectively protect the surface of the material which is originally easy to corrode, pollute and damage. Aluminum materials are widely used in the fields of electric appliances, buildings, vehicles, machine manufacturing, defense industry, and the like because of their excellent properties. However, since elemental aluminum has high reactivity, the surface thereof is easily contaminated with dirt and chemically corroded. The super-hydrophobic coating prepared on the surface of the aluminum material can effectively improve the performances of pollution resistance, corrosion resistance and the like of the surface of the aluminum material and realize the functional application of the surface of the aluminum material.
According to the existing surface wetting theory, for intrinsic hydrophilic materials (such as aluminum, copper, zinc, magnesium and the like), the basic preparation process of the super-hydrophobic coating comprises the following steps: firstly, increasing the roughness of the surface of a substrate; secondly, a substance having a low surface energy is modified on the surface of the substrate having increased roughness. Studies have shown that on relatively smooth surfaces, modifying only low surface energy substances only increases their static contact angle value with water to 119 ° at best. Therefore, the key point of artificially preparing the super-hydrophobic material is to construct a surface rough structure with a micro-or even nano-structure, such as a crown structure, a columnar structure, a hierarchical structure with multiple roughness, and the like.
Currently, there are many methods for improving the surface roughness, such as chemical etching, laser etching, sol-gel method, vapor deposition, electrochemical method, and the like. In recent years, ultrafine particles of transition metals and oxides thereof have been widely used in the fields of catalysis, superconduction, sensing, magnetic storage, and the like. Wherein the copper oxide is a narrow band gap (forbidden band width E)g1.2Ev), and the P-type semiconductor material is widely applied to the fields of solar cells, catalysis of organic reaction, lithium batteries, biosensing, gas sensing, field emission, photocatalytic degradation of organic pollutants, magnetic storage devices and the like due to unique physical and chemical characteristics; as is well known, nanomaterials have physical and chemical properties different from those of bulk materials, and these physical and chemical properties largely depend on the size and morphology of the materials, and micro/nano structure units with different morphologies are also basic modules for constructing nano devices; therefore, it is a promising research to prepare copper oxide rough structures on related materials and realize the functional application of the copper oxide rough structures.
Chinese patent (publication No. CN105505204A, publication No. 2016, 4 and 20) discloses a preparation method of a nano copper oxide super-hydrophobic coating. According to the method, the surface of copper oxide nanoparticles is modified by using low-surface-energy material mercaptan (n-octyl mercaptan, octadecyl mercaptan) or stearic acid, the modified copper oxide nanoparticles and silicon rubber are respectively dissolved in isopropanol to prepare the coating of a component a and a component b, and the components a and b are mixed according to the volume ratio of 0.5-1.5: 1 to prepare the super-hydrophobic coating. The method has strict requirements on raw materials, and the application threshold of the patent is improved. Chinese patent (publication No. CN104829143A, published as 2015, 8 and 12) discloses a preparation method of a nano copper oxide super-hydrophobic film. Firstly, preparing nanometer copper oxide with a corolla-shaped crystal morphology by using a liquid phase precipitation method, and specifically, stirring at the temperature of 60-85 ℃ to prepare a mixed solution a of hexadecyl trimethylamine ammonium bromide and copper sulfate, adjusting the pH value of the mixed solution a to 12 by using a sodium hydroxide solution with a certain concentration, stirring for 8-12h, drying black precipitate obtained by vacuum filtration in a vacuum drying oven at the temperature of 60-90 ℃ for 1-2h, and grinding to obtain copper oxide; dispersing copper oxide into deionized water, adding an organic silicon defoaming agent, uniformly spraying the organic silicon defoaming agent on a glass slide through a spray gun, and drying the glass slide in a vacuum drying oven at 60-90 ℃ to prepare the glass slide with the surface coated with the nano copper oxide; and finally, preparing the nano copper oxide super-hydrophobic film after modification by adopting a low-surface-energy substance stearic acid ethanol solution. The invention mainly depends on the pH value to regulate and control the quantitative proportion of the copper sulfate and the sodium hydroxide in the reaction system, and the change of reaction products is caused when the pH value is too large or too small, so the invention has strict control on related experimental conditions. Chinese patent (publication No. CN104726875A, published as 2015 6-24) discloses a method for preparing a super-hydrophobic copper oxide film on the surface of steel, firstly, electrodepositing copper on the surface of steel to form a non-smooth copper plating layer; forming a copper oxide film on the surface of the copper plating layer through hydrothermal treatment; and finally, obtaining the copper oxide film with the super-hydrophobic function through fluorination treatment. The method has strict requirements on experimental parameters in the electroplating and hydrothermal oxidation treatment processes, and the copper oxide film formed by the hydrothermal oxidation treatment is limited by the heating liquid oxidation film forming mode, so that the copper oxide structure is loose, the preparation period is long, and the method is not suitable for large-scale production and practical application. Chinese patent (publication No. CN107522161A, published as 2017, 12 and 29) discloses a copper-based super-hydrophobic surface with a controllable micro-nano structure and a preparation method thereof. Firstly, performing laser etching on the surface of a red copper substrate to construct a square, triangular or strip-shaped groove micron structure array; growing a nanowire on the surface in a thermal oxidation mode; and finally standing in the air for more than one week to obtain the copper-based super-hydrophobic surface with the controllable micro-nano structure. The laser etching process of the method has high dependence on equipment and high power consumption, and is not suitable for large-scale production and application. Chinese patent publication No. CN101476121A, published as 2009, 7/8) discloses a method for preparing a superhydrophobic film on a copper surface by using a low pressure oxidation method. The method comprises the steps of preparing a layer of copper hydroxide film on the surface of a copper sheet by a conventional inorganic chemical method, and then carrying out oxidative decomposition treatment on the copper hydroxide film on the surface of the copper sheet by a low-pressure oxidation method to obtain the copper oxide super-hydrophobic film with a double-layer micro-nano structure, wherein the upper layer of the copper oxide super-hydrophobic film is of a micro flower-like structure, and the lower layer of the copper oxide super-hydrophobic film is of a nano-. The method is only suitable for preparing the copper oxide super-hydrophobic film on the surface of copper, the proportion of potassium hydroxide and potassium persulfate is strict, and the preparation process has higher requirements on experimental parameters, so that the large-scale production of the copper oxide super-hydrophobic film is limited. Chinese patent (publication No. CN104357827A, publication No. 2015, 2 and 18) discloses a preparation method of a super-hydrophobic corrosion-resistant copper-based super-hydrophobic surface. Firstly, putting a cleaned copper sheet and ammonia water solution with a certain concentration into a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting at the temperature of 60-120 ℃, keeping the temperature for 3-24 hours, taking out, washing with deionized water, and drying with nitrogen; and then soaking the copper sheet in ethanol solutions of sulfuric acids with different branched chains for 6-24h to obtain the super-hydrophobic copper sheet with the surface having a nanorod, nano needle, nano sheet and petal-shaped structure. However, the invention mainly prepares a series of copper oxide structures by a hydrothermal growth mode, and the whole closed reaction container can generate high temperature and high pressure and a large amount of reaction byproducts and gas volatile matters in the reaction process, so that the requirements on the tightness and safety of the container in actual production are higher, and the closed reaction container is not suitable for large-scale production. Chinese patent (publication No. CN101864571A, published as 10/20/2010) discloses a method for preparing a copper-based superhydrophobic surface. Firstly, etching a copper-based surface in a nitric acid solution for a while, taking out, then uniformly spraying acetic acid, and spraying acetic acid again after drying in the shade for 24 hours at room temperature and with relative humidity of more than 50 percent to form a surface layer distributed all over green spots; then putting the surface into a baking oven at 300 +/-50 ℃ for baking and taking out, and cooling in air; and finally, soaking the sample in an ethanol solution of n-octadecanethiol or dodecanethiol with a certain concentration in a water bath at 40-60 ℃ to prepare the super-hydrophobic surface. According to the copper sheet and the preparation method thereof, copper oxide with different structures is prepared on the surface of the copper sheet by mainly utilizing a mode of decomposing the copper verdigris at high temperature, so that the copper oxide on the surface is weakly combined with the copper sheet, and the requirement on environmental conditions in the early stage of the copper verdigris preparation process is higher, so that the copper sheet and the preparation method thereof are not suitable for large-scale production and practical application.
The copper oxide with the dendritic micro-nano structure is prepared through simple processes of chemical replacement and direct thermal oxidation, and the super-hydrophobic coating can be prepared on the aluminum substrate by combining with a low-energy modification process. The preparation method has the advantages of simple process, low cost and stable structure of the prepared copper oxide; the super-hydrophobic coating prepared by combining the low-energy modification process has good self-cleaning property, thermal stability and the like. In addition, the method can be applied to the surfaces of aluminum materials, magnesium, zinc, iron and other metal materials, and is suitable for industrial production.
Disclosure of Invention
The invention aims to develop a method for simply and quickly preparing a copper oxide super-hydrophobic coating with a dendritic micro-nano structure, and the method is adopted to prepare the copper oxide coating with super-hydrophobicity on the surface of an aluminum alloy substrate, so that the surface of the aluminum alloy has the functions of super-hydrophobicity, corrosion resistance, scaling prevention and self-cleaning, and the service life of the aluminum alloy is prolonged.
In order to achieve the purpose, the specific process flow of the invention is as follows:
1. pretreatment of an aluminum substrate: polishing the processed aluminum sample smoothly by using metallographic waterproof abrasive paper (polishing from No. 300 to No. 2000 step by step), and sequentially putting the polished sample into acetone and absolute ethyl alcohol for ultrasonic cleaning for 5-15min to remove grease and pollutants on the surface of the sample; and then sequentially carrying out surface alkali cleaning oxidation film removal and acid cleaning treatment on the cleaned aluminum material substrate sample: the step of alkali washing to remove an oxidation film is to put the polished smooth aluminum product sample into an alkaline water washing liquid containing 3% -10% of sodium hydroxide for room temperature treatment for 1-2min, and then clean the aluminum product sample with absolute ethyl alcohol; the pickling treatment is to wash the aluminum product sample subjected to alkaline washing to remove an oxide film by using a pickling solution containing 20-30% of nitric acid, clean the aluminum product sample by using absolute ethyl alcohol and dry the aluminum product sample for later use;
2. chemical displacement reaction deposition of copper layer: preparing 30-150g/LCuCl of2·2H2O water solution, or CuSO with the concentration of 20-120g/L4·5H2O and FeCl of 2.5-40g/L3·6H2O (or 5-60g/L NaCl), immersing the aluminum material sample cleaned in the step 1 into the prepared mixed solution for chemical replacement reaction, wherein the reaction time is 0.5-5 min; then soaking the reacted sample into a proper amount of clear water (1-2L) for 10-20min, and removing the residual reaction liquid on the surface; then putting the sample into a drying oven to be dried at 50-150 ℃;
3. thermal oxidation treatment: placing the aluminum material sample with the copper deposition layer covered on the surface in the step 2 into a tubular furnace (or a muffle furnace) for heat treatment, wherein the gas atmosphere is air, the heating rate is 2-6 ℃/min, the heat treatment temperature is 300-600 ℃, the heat preservation time is 1-5h, and after the heat treatment is finished, taking out the aluminum material sample and air-cooling the aluminum material sample to the room temperature;
4. low-energy modification: and (3) putting the sample obtained in the step (3) into 0.005-0.05mol/L of anhydrous ethanol solution of low-energy substances (stearic acid, palmitic acid, lauric acid and perfluorooctanoic acid) for soaking for 1-5h, taking out and putting into a culture dish, and then putting into a drying oven for drying at 50-120 ℃ to obtain the copper oxide super-hydrophobic coating with the dendritic microstructure on the surface.
And (3) dropping deionized water on the obtained copper oxide super-hydrophobic surface to measure contact angles, wherein the contact angles are all larger than 150 degrees, and the rolling angle is smaller than 10 degrees. In addition, the super-hydrophobic surface can still maintain the super-hydrophobicity after being placed in the air for more than 9 months, and after being taken out after being soaked in water for 1 month, the contact angle of the super-hydrophobic surface is still larger than 150 degrees, and the rolling angle of the super-hydrophobic surface is smaller than 10 degrees.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method directly generates the copper oxide coating with the micro-nano structure on the copper coating with the micro-nano structure in situ in a direct thermal oxidation mode, and is simple and easy to implement.
(2) The preparation method disclosed by the invention is low in production cost, high in production efficiency and easy to realize industrial production.
(3) The processing process adopted by the invention has no special requirements on the shape and the size of the sample, increases the popularization and application of the invention, and can be popularized to the surfaces of other metal materials such as magnesium, zinc, iron and the like.
Drawings
FIG. 1 is an SEM image of a copper oxide superhydrophobic surface;
FIG. 2 is a contact angle and a rolling angle of a deionized water drop on a copper oxide super-hydrophobic coating;
FIG. 3 is a graph of the relationship between the duration of immersion of a copper oxide superhydrophobic surface in water and the contact angle and the rolling angle;
FIG. 4 is a graph showing the relationship between the holding time of the copper oxide superhydrophobic surface at 200 ℃ and the contact angle and the rolling angle;
FIG. 5 is a schematic of the self-cleaning performance of a copper oxide superhydrophobic surface.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The invention is described in detail below with reference to the attached drawing figures:
the invention aims to develop a method for simply and quickly preparing a copper oxide super-hydrophobic coating on the surface of an aluminum material, and the service life of the aluminum material is prolonged by virtue of the inherent hydrophobic, anti-corrosion, anti-scaling and self-cleaning functions of the super-hydrophobic surface.
In order to achieve the purpose, pure aluminum and 6061 aluminum alloy are taken as research objects, and the copper oxide super-hydrophobic coating is prepared on the surfaces of the aluminum and the aluminum alloy.
The first embodiment is as follows:
(1) selecting pure aluminum with the size of 20 multiplied by 40 multiplied by 2mm as a substrate sample, polishing the substrate sample smoothly by metallographic waterproof abrasive paper, and sequentially putting the polished sample into acetone and absolute ethyl alcohol for ultrasonic cleaning for 5min to remove grease and pollutants on the surface of the sample;
(2) immersing the cleaned pure aluminum sample into alkaline water washing liquid containing 3% of sodium hydroxide (room temperature) for treatment for 2min, and cleaning the sample by using absolute ethyl alcohol; washing with a pickling solution of 20% nitric acid, washing with absolute ethyl alcohol, and drying to realize the oxidation film removal and activation treatment of the pure aluminum surface;
(3) immersing the treated pure aluminum sample into CuCl containing 50g/L2·2H2In an aqueous O solution, the chemical replacement time is4.5min, immersing the reacted surface in 1L of clear water for 20min, removing residual reaction liquid, and then putting the sample into a drying oven to be dried at 80 ℃ to obtain a pure aluminum sample with the surface covered with a copper deposition layer with the shape of a dendritic micro-nano structure;
(4) putting the sample obtained in the step (3) into a muffle furnace for heat treatment, wherein the heating rate is 3 ℃/min, the heat treatment temperature is 300 ℃, the heat preservation time is 2h, taking out the sample after the heat treatment is finished, and cooling the sample to room temperature in air;
(5) soaking the sample obtained in the step (4) in 0.01mol/L stearic acid absolute ethyl alcohol solution for 2h, taking out the sample, placing the sample in a culture dish, and drying the sample in a drying box at 60 ℃ to obtain a copper oxide super-hydrophobic coating (shown in figure 1) with the surface having the dendritic micro-nano structure; the contact angle of a 3 mul deionized water droplet on the copper oxide superhydrophobic surface was about 159.64 deg., and the roll off angle was about 4.5 deg. (as shown in figure 2).
(6) The prepared copper oxide super-hydrophobic surface is completely soaked in clear water for a period of time (5 days, 10 days, 15 days, 20 days, 25 days and 30 days), and the contact angle and the rolling angle of a 3 mu L deionized water drop on the super-hydrophobic surface are measured according to the relation with the soaking time (as shown in figure 3). After the super-hydrophobic surface is completely soaked in clear water for 30 days, the water contact angle value is about 159.41 degrees, and the rolling angle is about 4.6 degrees, so that the super-hydrophobic surface can keep the contact angle and the rolling angle stability for a long time in the clear water.
(7) The prepared copper oxide superhydrophobic surface is placed in a heating furnace at 200 ℃ for heat preservation for a period of time (3 hours, 6 hours, 9 hours and 12 hours), and the relation between the contact angle and the rolling angle of a 3 mu L deionized water drop on the superhydrophobic surface and the soaking time is measured (as shown in figure 4). After the super-hydrophobic surface is kept for 12 hours, the water contact angle value of the super-hydrophobic surface is about 159.60 degrees, the rolling angle is about 4.8 degrees, and the super-hydrophobic surface is proved to be capable of keeping the contact angle and the rolling angle stable for a long time below 200 ℃.
(8) A certain amount of floating bead powder with the particle size of 100-150 mu m is uniformly paved on the super-hydrophobic surface, the super-hydrophobic surface is inclined by about 8 degrees, then 10 mu L of deionized water is dripped on the surface at the height of about 5cm, and the deionized water drips the floating bead powder covered on the surface easily (as shown in figure 5), so that the super-hydrophobic surface is proved to have good self-cleaning performance.
The second embodiment is as follows:
(1) selecting a 6061 aluminum alloy with the size of 20 multiplied by 40 multiplied by 2mm as a substrate sample, polishing the substrate sample smoothly by using metallographic waterproof abrasive paper, and sequentially putting the polished sample into acetone and absolute ethyl alcohol for ultrasonic cleaning for 10min to remove grease and pollutants on the surface of the sample;
(2) soaking the cleaned 6061 aluminum alloy sample into alkaline water washing liquid containing 10% of sodium hydroxide (at room temperature) for treatment for 1min, and cleaning the sample by using absolute ethyl alcohol; washing with 30% nitric acid pickling solution, washing with absolute ethyl alcohol, and drying to realize the oxidation film removal and activation treatment of the 6061 aluminum alloy surface;
(3) the treated 6061 aluminum alloy sample is immersed into CuSO with the concentration of 25g/L4·5H2O and 5g/L FeCl3·6H2In the O aqueous solution, the chemical replacement time is 4min, then the surface after reaction is immersed in 1L of clear water for 15min, and the residual reaction solution is removed; then, putting the sample into a drying oven to be dried at 100 ℃ to obtain a copper coating with the surface having the dendritic microstructure;
(4) putting the 6061 aluminum alloy sample with the copper deposition layer covered on the surface obtained in the step (3) into a muffle furnace for heat treatment, wherein the heating rate is 3 ℃/min, the heat treatment temperature is 400 ℃, the heat preservation time is 4h, taking out the 6061 aluminum alloy sample after the heat treatment is finished, and air cooling the 6061 aluminum alloy sample to the room temperature;
(5) and (3) placing the sample obtained in the step (4) into a palmitic acid absolute ethyl alcohol solution with the concentration of 0.02mol/L for soaking for 2h, taking out the sample, placing the sample into a culture dish, and placing the culture dish into a drying oven to be dried at the temperature of 60 ℃ to obtain the super-hydrophobic surface. The contact angle of deionized water drops on the copper oxide super-hydrophobic surface is about 158.76 degrees, and the rolling angle is about 5.2 degrees.
The third concrete embodiment:
(1) selecting a 6061 aluminum alloy with the size of 20 multiplied by 40 multiplied by 2mm as a substrate sample, polishing the substrate sample smoothly by using metallographic waterproof abrasive paper, and sequentially putting the polished sample into acetone and absolute ethyl alcohol for ultrasonic cleaning for 20min to remove grease and pollutants on the surface of the sample;
(2) soaking the cleaned 6061 aluminum alloy sample into alkaline water washing liquid containing 8% of sodium hydroxide (at room temperature) for treatment for 1.3min, and cleaning the sample by using absolute ethyl alcohol; washing with 25% nitric acid pickling solution, washing with absolute ethyl alcohol, and drying to realize the oxidation film removal and activation treatment of the 6061 aluminum alloy surface;
(3) the treated 6061 aluminum alloy sample is immersed into CuSO with the concentration of 25g/L4·5H2O and 10g/L NaCl water solution, the chemical replacement time is 4min, then the surface after reaction is immersed in 1.5L clear water for 20min, and residual reaction liquid is removed; then, putting the sample into a drying oven to be dried at the temperature of 80 ℃ to obtain a copper coating with the dendritic microstructure on the surface;
(4) putting the 6061 aluminum alloy sample with the copper deposition layer covered on the surface obtained in the step (3) into a muffle furnace for heat treatment, wherein the heating rate is 4 ℃/min, the heat treatment temperature is 500 ℃, the heat preservation time is 3h, taking out the 6061 aluminum alloy sample after the heat treatment is finished, and air cooling the 6061 aluminum alloy sample to the room temperature;
(5) and (3) placing the sample obtained in the step (4) into a 0.04mol/L lauric acid absolute ethyl alcohol solution for soaking for 2h, taking out the sample, placing the sample into a culture dish, and placing the culture dish into a drying box to be dried at 60 ℃ to obtain the super-hydrophobic surface. The contact angle of deionized water drops on the copper oxide super-hydrophobic surface is about 158.97 degrees, and the rolling angle is 4.8 degrees.
The fourth concrete embodiment:
(1) selecting a 6061 aluminum alloy with the size of 20 multiplied by 40 multiplied by 2mm as a substrate sample, polishing the substrate sample smoothly by using metallographic waterproof abrasive paper, and sequentially putting the polished sample into acetone and absolute ethyl alcohol for ultrasonic cleaning for 15min to remove grease and pollutants on the surface of the sample;
(2) soaking the cleaned 6061 aluminum alloy sample into alkaline water washing liquid containing 6% of sodium hydroxide (at room temperature) for treatment for 1.5min, and cleaning the sample by using absolute ethyl alcohol; washing with 30% nitric acid pickling solution, washing with absolute ethyl alcohol, and drying to realize the oxidation film removal and activation treatment of the 6061 aluminum alloy surface;
(3) immersing the treated 6061 aluminum alloy sample into CuSO with the concentration of 50g/L4·5H2O and 30g/L NaCl water solution, the chemical replacement time is 3.5min, then the surface after reaction is immersed in 2L clear water for 20min, and the residual reaction liquid is removed; then, putting the sample into a drying oven to be dried at the temperature of 80 ℃ to obtain a copper coating with the dendritic microstructure on the surface;
(4) putting the 6061 aluminum alloy sample with the copper deposition layer covered on the surface obtained in the step (3) into a muffle furnace for heat treatment, wherein the heating rate is 5 ℃/min, the heat treatment temperature is 500 ℃, the heat preservation time is 2 hours, taking out the 6061 aluminum alloy sample after the heat treatment is finished, and air cooling the 6061 aluminum alloy sample to the room temperature;
(5) and (3) placing the sample obtained in the step (4) into a perfluorooctanoic acid absolute ethyl alcohol solution with the concentration of 0.05mol/L for soaking for 3 hours, taking out the sample, placing the sample into a culture dish, and placing the culture dish into a drying box to be dried at the temperature of 60 ℃ to obtain the super-hydrophobic surface. The contact angle of deionized water drops on the copper oxide super-hydrophobic surface is about 159.31 degrees, and the rolling angle is 4.6 degrees.
Claims (1)
1. A method for preparing a copper oxide super-hydrophobic coating with a dendritic micro-nano structure is characterized by comprising the following steps:
(1) pretreatment of an aluminum substrate: polishing the processed aluminum sample step by using 300# to 2000# metallographic waterproof abrasive paper, and sequentially putting the polished sample into acetone and absolute ethyl alcohol for ultrasonic cleaning for 5-15min to remove grease and pollutants on the surface of the sample; and then sequentially carrying out surface alkali washing oxidation film removal and acid washing activation treatment on the cleaned aluminum material substrate sample: the step of alkali washing to remove an oxidation film is to put the polished smooth aluminum product sample into an alkaline water washing liquid containing 3% -10% of sodium hydroxide for room temperature treatment for 1-2min, and then clean the aluminum product sample with absolute ethyl alcohol; the acid washing and activating treatment is to wash the aluminum material sample after the oxide film is removed by alkali washing with acid washing solution of 20-30% nitric acid, clean the aluminum material sample with absolute ethyl alcohol and dry the aluminum material sample for later use;
(2) chemical displacement reaction deposition of copper layer: preparing 30-150g/L CuCl2·2H2O aqueous solution, or Cu of 20-120g/LSO4·5H2O and FeCl of 2.5-40g/L3·6H2Mixed water solution of O, or prepared CuSO with concentration of 20-120g/L4·5H2Soaking the aluminum material sample cleaned in the step (1) into the prepared mixed solution for chemical replacement reaction, wherein the mixed solution consists of O and 5-60g/L NaCl, and the reaction time is 0.5-5 min; then soaking the reacted sample in 1-2L of clear water for 10-20min, and removing residual reaction liquid; then putting the sample into a drying oven to be dried at 50-150 ℃;
(3) thermal oxidation treatment: placing the aluminum material sample covered with the copper deposition layer on the surface in the step (2) into a tubular furnace or a muffle furnace for heat treatment, wherein the gas atmosphere is air, the heating rate is 2-6 ℃/min, the heat treatment temperature is 300-600 ℃, the heat preservation time is 1-5h, and after the heat treatment is finished, taking out the aluminum material sample and air-cooling the aluminum material sample to the room temperature;
(4) low-energy modification: and (3) putting the sample obtained in the step (3) into 0.005-0.05mol/L stearic acid absolute ethyl alcohol solution for soaking for 1-5h, taking out and putting into a culture dish, and then putting into a drying oven for drying at 50-120 ℃ to obtain the copper oxide super-hydrophobic surface coating with the dendritic micro-nano structure morphology, wherein the low-energy substance can be palmitic acid, lauric acid or perfluorooctanoic acid.
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