CN111822296A - Preparation method of super-hydrophobic composite coating on surface of aluminum alloy - Google Patents

Preparation method of super-hydrophobic composite coating on surface of aluminum alloy Download PDF

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CN111822296A
CN111822296A CN202010695661.6A CN202010695661A CN111822296A CN 111822296 A CN111822296 A CN 111822296A CN 202010695661 A CN202010695661 A CN 202010695661A CN 111822296 A CN111822296 A CN 111822296A
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aluminum alloy
preparation
composite coating
coating
super
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夏晓健
嫣庆锰
林德源
尹元
李扬森
洪毅成
蔡建宾
韩纪层
陈云翔
万芯瑗
陈天鹏
郑勇
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Nanjing University of Aeronautics and Astronautics
Electric Power Research Institute of State Grid Fujian Electric Power Co Ltd
State Grid Fujian Electric Power Co Ltd
Putian Power Supply Co of State Grid Fujian Electric Power Co Ltd
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Nanjing University of Aeronautics and Astronautics
Electric Power Research Institute of State Grid Fujian Electric Power Co Ltd
State Grid Fujian Electric Power Co Ltd
Putian Power Supply Co of State Grid Fujian Electric Power Co Ltd
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Priority to CN202010695661.6A priority Critical patent/CN111822296A/en
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    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
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    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
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Abstract

The invention relates to a preparation method of a super-hydrophobic composite coating on the surface of an aluminum alloy, belonging to the field of surface treatment of metal materials. The method comprises the following specific steps: ultrasonically cleaning the surface of the aluminum alloy; carrying out phosphoric acid anodic oxidation treatment on the surface of the aluminum alloy; to SiO2Performing hydrophobic modification treatment to prepare coating, wherein the coating raw material comprises modified SiO2Acetic acid ethyl esterEster, epoxy resin, fluorine-containing polyurethane, fluorine-silicon varnish and isophorone diamine; then spraying the aluminum alloy on the surface of the aluminum alloy; and curing at room temperature to obtain the super-hydrophobic composite coating. The water contact angle of the super-hydrophobic composite coating on the surface of the aluminum alloy prepared by the invention is more than 155 degrees, the rolling angle is below 7 degrees, and the combination between the super-hydrophobic composite coating and a matrix is good. The preparation method has simple process, no special requirements on production equipment and lower production cost, and is beneficial to industrial popularization and application.

Description

Preparation method of super-hydrophobic composite coating on surface of aluminum alloy
Technical Field
The invention relates to a preparation method of a super-hydrophobic composite coating on the surface of an aluminum alloy, belonging to the field of surface treatment of metal materials.
Background
The aluminum alloy is widely applied to various fields such as electric power, buildings, traffic, aviation, mechanical manufacturing, household appliances and the like. Under normal conditions, the aluminum alloy has better corrosion resistance, because a passive film naturally formed on the surface of the aluminum alloy has a certain protection effect on the aluminum alloy. However, the surface of the aluminum alloy is passivated with film pair Cl-The ions are very sensitive. High atmospheric humidity and Cl in coastal areas-The ion content is high, and the passive film on the surface of the aluminum alloy is easy to damage, so that a corrosion battery is formed, and serious corrosion can occur in a short time. In order to slow down or hinder the corrosion of the aluminum alloy in the marine atmospheric environment, the aluminum alloy part needs to be subjected to corresponding corrosion protection treatment.
At present, the protection method for the aluminum alloy mainly comprises electrochemical protection, corrosion inhibitors, surface oxidation treatment, protective coatings and the like. Among them, the use of anticorrosive coatings is the most widely and conveniently applied method at present. However, most of the painting or spraying of the protective coating is carried out on site after the aluminum alloy component is installed, so that the uniformity and consistency of the protective effect of the coating are difficult to ensure, and the factors causing the defects of the coating are many, so that the actual implementation effect often cannot be expected. Corrosion inhibitor protected in Cl-The corrosion prevention effect of coastal areas with high ion content is limited, and the method is not suitable for long-term corrosion prevention. The oxidation treatment is to form an oxide layer on the surface of the aluminum alloy to play a role in corrosion prevention, but because the formed oxide film often contains micropores with different sizes, although the corrosion prevention performance can be improved through hole sealing treatment, the Cl is treated for a long time-When the aluminum alloy is used in coastal areas with high ion content, the protective film can be damaged, so that the aluminum alloy is corroded. Because the aluminum alloy has lower potential and is relatively active, the electrochemical protection is carried out independentlyIt is difficult.
The super-hydrophobic technology is a novel and environment-friendly metal surface treatment technology, and has the advantages of wide application range, no environmental pollution and the like compared with the traditional corrosion protection methods such as cathode protection, corrosion inhibitor protection and the like. Related researches report that the preparation of the aluminum alloy surface super-hydrophobic coating can greatly reduce the self-corrosion current density, thereby greatly reducing the corrosion speed of aluminum alloy parts and having great application prospect in the field of corrosion protection.
At present, the technologies for preparing the aluminum alloy super-hydrophobic surface mainly include a chemical etching method, a plasma etching method, a laser etching method, a vapor deposition method, a sol-gel method, a template method, an electrostatic spinning method, a nano-array method, a self-assembly method, an electrochemical anodic oxidation method and the like. Researchers at home and abroad can prepare super-hydrophobic surfaces by respectively adopting the technologies through systematic research, the contact angle of water drops on the solid surface can reach more than 150 degrees, and the rolling angle can be as low as less than 10 degrees. The main technical characteristics of the methods for preparing the super-hydrophobic surface of the metal material are that firstly, a rough surface with a micro-nano structure is constructed, and then, the rough surface is further modified by adopting a low-surface-energy substance.
However, the method either needs expensive equipment, or the preparation process is complex, or the process needs precise control, or the prepared surface super-hydrophobic coating has weak bonding force with a substrate and is easy to damage, thereby severely limiting the application of the aluminum alloy super-hydrophobic surface preparation technology in actual production.
In view of the above, in order to apply the superhydrophobic surface preparation technology to industrial production, it is necessary to develop a new method for preparing a superhydrophobic surface of an aluminum alloy, which is simple, convenient, easy, excellent in comprehensive performance, and low in cost, so that the method can be suitable for industrial production.
Disclosure of Invention
The invention aims to provide a preparation method of a super-hydrophobic composite coating on the surface of an aluminum alloy, which is simple, convenient and easy to implement, excellent in comprehensive performance and low in cost.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a super-hydrophobic composite coating on the surface of an aluminum alloy comprises the following steps:
step (1), cleaning the surface of the aluminum alloy: ultrasonically cleaning the surface of the aluminum alloy by using ethanol and deionized water in sequence to remove surface oil stains;
step (2), phosphoric acid anodic oxidation treatment of the surface of the aluminum alloy: firstly, preparing a phosphoric acid aqueous solution with the mass concentration of 10-14 wt.%; putting the solution into an anodic oxidation tank, putting an aluminum alloy part into an anode, electrifying a cathode by adopting stainless steel to carry out anodic oxidation treatment; after the treatment is finished, taking out the aluminum alloy part, and washing the aluminum alloy part by running water; then drying;
step (3), for SiO2Carrying out hydrophobic modification treatment: mixing nano SiO2Putting into ammonia water, and adding nanometer SiO2The mass ratio of the ammonia water to the ammonia water is 1: 6-1: 8, and ultrasonic dispersion is carried out for 30min to obtain mixed solution; mixing 1H,1H,2H, 2H-perfluorodecyl triethoxysilane (PFDTES, 96%, Shanghai Meclin reagent Co., Ltd.) with ethanol, wherein the concentration of PFDTES is 0.8-1.0 wt%, and stirring in a magnetic stirrer for 1H to obtain PFDTES ethanol mixed solution; then pouring the silicon dioxide ammonia water mixed solution into the PFDTES ethanol mixed solution, and fully stirring in a magnetic stirrer; then placing the mixture into a centrifuge for centrifugal treatment; the centrifuged SiO2The colloid is put into a vacuum drying oven for drying.
Step (4), surface coating and preparing a composite coating: with hydrophobically modified SiO2Ethyl acetate, epoxy resin, fluorine-containing polyurethane, fluorine-containing silicon varnish and isophorone diamine are used as raw materials to prepare a coating; ultrasonically dispersing for 30min to mix uniformly; spraying the coating on the surface of the aluminum alloy subjected to phosphoric acid anodic oxidation treatment at a constant speed under 0.4MPa by using a spray gun; after the spraying is finished, the coating is cured for 24 hours at room temperature, and the super-hydrophobic composite coating can be prepared on the surface of the aluminum alloy.
Further, in the step (2), the voltage of the phosphoric acid anodic oxidation treatment is 10-12V, and the time is 20-25 min.
Further, in the step (3), the concentration of the ammonia water is 5-6 wt%.
Further, in the step (3), the silica ammonia water mixed solution is poured into the PFDTES ethanol mixed solution, the mass ratio of the silica ammonia water mixed solution to the PFDTES ethanol mixed solution is 1:3.2 to 1:3.8, the stirring time in a magnetic stirrer is 20-30h, and the temperature is 40-50 ℃.
Further, in the step (3), when the centrifuge is used for centrifugation, the rotation speed of the centrifuge is 4000-.
Further, in the step (3), the vacuum drying time is 10-15h, and the temperature is 60-70 ℃.
Further, in the step (4), the coating comprises the following raw materials in parts by weight: modified SiO21.5 to 2.5 percent of ethyl acetate, 1.5 to 2.5 percent of epoxy resin, 0.4 to 0.8 percent of fluorine-containing polyurethane, 1.2 to 2.0 percent of fluorine-silicon varnish and 0.6 to 1.0 percent of isophorone diamine.
Further, in the step (4), the epoxy resin is obtained from Wuhan Fulaide paint GmbH under the brand number of 1003F; the fluorinated polyurethane was purchased from Wuhan Fulaide coatings Co., Ltd, under the designation F909 type; the fluorosilicone varnish was purchased from Wuhan Fulaide coatings Co., Ltd, and was brand F808.
The invention has the beneficial effects that:
(1) the invention adopts phosphoric acid anode oxidation treatment to treat the surface of the aluminum alloy, a porous structure is formed on the surface, the cell diameter of the porous structure is larger than that of other treatment methods, a coating solution with certain viscosity is easy to permeate into micropores, and the binding force between the surface coating and a substrate is greatly increased by the mechanical embedding effect.
(2) The raw materials are easy to obtain, low in price and safe and nontoxic.
(3) The preparation steps are simple, convenient and easy to implement, no special requirements are required for production equipment, only conventional equipment is required, and industrial popularization and application are facilitated.
(4) The aluminum alloy surface super-hydrophobic composite coating prepared by the method has good performance, the contact angle is larger than 155 degrees, the rolling angle is below 7 degrees, and the surface uniformity is good.
Drawings
FIG. 1 is a water contact angle graph of a super-hydrophobic composite coating on the surface of an aluminum alloy obtained in example 1;
FIG. 2 is a water contact angle graph of the super-hydrophobic composite coating on the surface of the aluminum alloy obtained in example 2;
FIG. 3 is a water contact angle graph of the super-hydrophobic composite coating on the surface of the aluminum alloy obtained in example 3;
FIG. 4 is an SEM topography of the super-hydrophobic composite coating on the surface of the aluminum alloy obtained in example 1;
FIG. 5 is an SEM topography of the super-hydrophobic composite coating on the surface of the aluminum alloy obtained in example 2;
FIG. 6 is an SEM topography of the super-hydrophobic composite coating on the surface of the aluminum alloy obtained in example 3.
Detailed Description
The present invention will be further explained with reference to examples.
The present invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the specific material ratios, process conditions and results thereof described in the examples are illustrative only and should not be taken as limiting the invention as detailed in the claims.
For the aluminum alloy surface super-hydrophobic composite coating prepared in the following examples, a contact angle measuring instrument is adopted to measure the static contact angle of the coating and simultaneously measure the rolling angle of the coating so as to represent the hydrophobic property of the coating.
Example 1:
(1) cleaning the surface of the aluminum alloy: ultrasonically cleaning with ethanol and deionized water for 5min, and blow-drying in air.
(2) Phosphoric acid anodic oxidation treatment on the surface of the aluminum alloy: firstly, preparing a phosphoric acid aqueous solution with the mass concentration of 10 wt%; putting the solution into an anodic oxidation tank, putting an aluminum alloy part at an anode, electrifying a cathode by adopting stainless steel for anodic oxidation treatment, wherein the voltage of phosphoric acid anodic oxidation treatment is 12V, and the time is 25 min; after the treatment is finished, taking out the aluminum alloy part, and washing the aluminum alloy part by running water; and then dried.
（3）SiO2Hydrophobic modification treatment: mixing nano SiO2Putting into ammonia water, and adding nanometer SiO2The mass ratio of the ammonia water solution to the ammonia water solution is 1:8, wherein the concentration of the ammonia water solution is 5wt%, and ultrasonic dispersion is carried out for 30min to obtain a mixed solution; PFDTES and ethanol are mixed, wherein the concentration of the PFDTES is 1.0 wt%, and the mixture is put into a magnetic stirrer to be stirred for 1 hour to obtain PFDTES ethanol mixed solution; then pouring the silicon dioxide ammonia water mixed solution into the PFDTES ethanol mixed solution, wherein the mass ratio of the silicon dioxide ammonia water mixed solution to the PFDTES ethanol mixed solution is 1:3.2, and stirring the mixture in a magnetic stirrer for 30 hours at the temperature of 50 ℃; then placing the mixture into a centrifugal machine for centrifugal treatment, wherein the rotating speed of the centrifugal machine is 5000rpm, and the time is 15 min; the centrifuged SiO2The colloid was dried in a vacuum oven for 15h at 60 ℃.
(4) Preparing a composite coating: with hydrophobically modified SiO2Ethyl acetate, epoxy resin, fluorine-containing polyurethane, fluorine-containing silicon varnish and isophorone diamine are used as raw materials to prepare the coating, and the raw materials of the coating are as follows in parts by mass: modified SiO21.5, 94.5 of ethyl acetate, 2 of epoxy resin, 0.4 of fluorine-containing polyurethane, 1.2 of fluorine-silicon varnish and 0.6 of isophorone diamine; and ultrasonically dispersing for 30min to uniformly disperse the mixed solution. The epoxy resin used was purchased from Wuhan Fulaide coatings Co., Ltd, brand 1003F; the fluorinated polyurethane was purchased from Wuhan Fulaide coatings Co., Ltd, under the designation F909 type; the fluorosilicone varnish was purchased from Wuhan Fulaide coatings Co., Ltd, and was brand F808.
(5) Surface coating: spraying the coating on the surface of the aluminum alloy subjected to phosphoric acid anodic oxidation treatment at a constant speed under 0.4MPa by using a spray gun, wherein the distance between the spray gun and the surface of the aluminum alloy workpiece is 25 cm; after the spraying is finished, the thickness of the coating is about 41 mu m, and the coating is solidified for 24 hours at room temperature to obtain the super-hydrophobic composite coating on the surface of the aluminum alloy.
Under the preparation process conditions, the static contact angle of the prepared aluminum alloy surface super-hydrophobic composite coating reaches 157 degrees, and the rolling angle is as low as 7 degrees. From the contact angle photographs, it can be seen that the water droplets dropped on the surface of the aluminum sheet had a spherical shape.
Example 2:
(1) cleaning the surface of the aluminum alloy: ultrasonically cleaning with ethanol and deionized water for 5min, and blow-drying in air.
(2) Phosphoric acid anodic oxidation treatment on the surface of the aluminum alloy: firstly, preparing a phosphoric acid aqueous solution with the mass concentration of 12 wt.%; putting the solution into an anodic oxidation tank, putting an aluminum alloy part at an anode, electrifying a cathode by adopting stainless steel for anodic oxidation treatment, wherein the voltage of phosphoric acid anodic oxidation treatment is 10V, and the time is 22 min; after the treatment is finished, taking down the aluminum alloy part, and washing the aluminum alloy part by running water; and then dried.
（3）SiO2Carrying out hydrophobic modification treatment: mixing nano SiO2Putting into ammonia water, and adding nanometer SiO2The mass ratio of the ammonia water to the ammonia water is 1:6, wherein the concentration of the ammonia water solution is 6wt%, and ultrasonic dispersion is carried out for 30min to obtain a mixed solution; PFDTES and ethanol are mixed, wherein the concentration of the PFDTES is 0.8 wt%, and the mixture is put into a magnetic stirrer to be stirred for 1 hour to obtain PFDTES ethanol mixed solution; then pouring the silicon dioxide ammonia water mixed solution into the PFDTES ethanol mixed solution, wherein the mass ratio of the silicon dioxide ammonia water mixed solution to the PFDTES ethanol mixed solution is 1:3.5, and stirring the mixture in a magnetic stirrer for 24 hours at the temperature of 40 ℃; then placing the mixture into a centrifugal machine for centrifugal treatment, wherein the rotating speed of the centrifugal machine is 4000rpm, and the time is 25 min; the centrifuged SiO2The colloid was dried in a vacuum oven for 10h at 70 ℃.
(4) Preparing a composite coating: with hydrophobically modified SiO2Ethyl acetate, epoxy resin, fluorine-containing polyurethane, fluorine-containing silicon varnish and isophorone diamine are used as raw materials to prepare the coating, and the raw materials of the coating are as follows in parts by mass: modified SiO22.0, 93.5 of ethyl acetate, 1.5 of epoxy resin, 0.6 of fluorine-containing polyurethane, 1.6 of fluorosilicone varnish and 0.8 of isophorone diamine; and ultrasonically dispersing for 30min to uniformly disperse the mixed solution. The epoxy resin used was purchased from Wuhan Fulaide coatings Co., Ltd, brand 1003F; the fluorinated polyurethane was purchased from Wuhan Fulaide coatings Co., Ltd, under the designation F909 type; the fluorosilicone varnish was purchased from Wuhan Fulaide coatings Co., Ltd, and was brand F808. .
(5) Surface coating: spraying the coating solution on the surface of the aluminum alloy subjected to phosphoric acid anodic oxidation treatment at a constant speed under 0.4MPa by using a spray gun, wherein the distance between the spray gun and the surface of the aluminum alloy workpiece is 25 cm; after the spraying is finished, the thickness of the coating is about 43 mu m, and the coating is solidified for 24 hours at room temperature to obtain the super-hydrophobic composite coating on the surface of the aluminum alloy.
Under the preparation process conditions, the static contact angle of the prepared aluminum alloy surface super-hydrophobic composite coating reaches 159 degrees, and the rolling angle is as low as 5 degrees. From the contact angle photographs, it can be seen that the water droplets dropped on the surface of the aluminum sheet had a spherical shape.
Example 3:
(1) cleaning the surface of the aluminum alloy: ultrasonically cleaning with ethanol and deionized water for 5min, and blow-drying in air.
(2) Phosphoric acid anodic oxidation treatment on the surface of the aluminum alloy: firstly, preparing a phosphoric acid aqueous solution with the mass concentration of 14 wt.%; putting the solution into an anodic oxidation tank, putting an aluminum alloy part at an anode, electrifying a cathode by adopting stainless steel for anodic oxidation treatment, wherein the voltage of phosphoric acid anodic oxidation treatment is 11V, and the time is 20 min; after the treatment is finished, taking down the aluminum alloy part, and washing the aluminum alloy part by running water; and then dried.
（3）SiO2Carrying out hydrophobic modification treatment: mixing nano SiO2Putting into ammonia water, and adding nanometer SiO2The mass ratio of the ammonia water to the ammonia water is 1:7, wherein the concentration of the ammonia water solution is 6wt%, and ultrasonic dispersion is carried out for 30min to obtain a mixed solution; PFDTES and ethanol are mixed, wherein the concentration of the PFDTES is 0.9wt%, and the mixture is put into a magnetic stirrer to be stirred for 1 hour to obtain PFDTES ethanol mixed solution; then pouring the silicon dioxide ammonia water mixed solution into the PFDTES ethanol mixed solution, wherein the mass ratio of the silicon dioxide ammonia water mixed solution to the PFDTES ethanol mixed solution is 1:3.8, and stirring the mixture in a magnetic stirrer for 20 hours at the temperature of 45 ℃; then placing the mixture into a centrifugal machine for centrifugal treatment, wherein the rotating speed of the centrifugal machine is 4500rpm, and the time is 20 min; the centrifuged SiO2The colloid was dried in a vacuum oven for 12h at 65 ℃.
(4) Preparing a composite coating: with hydrophobically modified SiO2Ethyl acetate, epoxy resin, fluorine-containing polyurethane, fluorine-containing silicon varnish and isophorone diamine are used as raw materials to prepare the coating, and the raw materials of the coating are as follows in parts by mass: modified SiO22.5, 92.5 of ethyl acetate, 2.5 of epoxy resin, 0.8 of fluorine-containing polyurethane, 2.0 of fluorosilicone varnish and 1.0 of isophorone diamine; and ultrasonically dispersing for 30min to uniformly disperse the mixed solution. The epoxy resin used was purchased from Wuhan Fulaide coatings Co., Ltd, brand 1003F; the fluorinated polyurethane was purchased from Wuhan Fulaide coatings Co., Ltd, under the designation F909 type; the fluorosilicone varnish was purchased from Wuhan Fulaide coatings Co., Ltd, and was brand F808.
(5) Surface coating: spraying the coating solution on the surface of the aluminum alloy subjected to phosphoric acid anodic oxidation treatment at a constant speed under 0.4MPa by using a spray gun, wherein the distance between the spray gun and the surface of the aluminum alloy workpiece is 25 cm; after the spraying is finished, the thickness of the coating is about 46 mu m, and the coating is solidified for 24 hours at room temperature to obtain the super-hydrophobic composite coating on the surface of the aluminum alloy.
Under the preparation process conditions, the static contact angle of the prepared aluminum alloy surface super-hydrophobic composite coating reaches 162 degrees, and the rolling angle is as low as 5 degrees. From the contact angle photographs, it can be seen that the water droplets dropped on the surface of the aluminum sheet had a spherical shape.
Comparative example 1:
(1) cleaning the surface of the aluminum alloy: ultrasonically cleaning with ethanol and deionized water for 5min, and blow-drying in air.
（2）SiO2Carrying out hydrophobic modification treatment: mixing nano SiO2Putting into ammonia water, and adding nanometer SiO2The mass ratio of the ammonia water to the ammonia water is 1:7, wherein the concentration of the ammonia water solution is 6wt%, and ultrasonic dispersion is carried out for 30min to obtain a mixed solution; PFDTES and ethanol are mixed, wherein the concentration of the PFDTES is 0.9wt%, and the mixture is put into a magnetic stirrer to be stirred for 1 hour to obtain PFDTES ethanol mixed solution; then pouring the silicon dioxide ammonia water mixed solution into the PFDTES ethanol mixed solution, wherein the mass ratio of the silicon dioxide ammonia water mixed solution to the PFDTES ethanol mixed solution is 1:3.8, and stirring the mixture in a magnetic stirrer for 20 hours at the temperature of 45 ℃; then placing the mixture into a centrifugal machine for centrifugal treatment, wherein the rotating speed of the centrifugal machine is 4500rpm, and the time is 20 min; after being centrifugedSiO of (2)2The colloid was dried in a vacuum oven for 12h at 65 ℃.
(3) Preparing a composite coating: with hydrophobically modified SiO2Ethyl acetate, epoxy resin, fluorine-containing polyurethane, fluorine-containing silicon varnish and isophorone diamine are used as raw materials to prepare the coating, and the raw materials of the coating are as follows in parts by mass: modified SiO22.5, 92.5 of ethyl acetate, 2.5 of epoxy resin, 0.8 of fluorine-containing polyurethane, 2.0 of fluorosilicone varnish and 1.0 of isophorone diamine; and ultrasonically dispersing for 30min to uniformly disperse the mixed solution. The epoxy resin used was purchased from Wuhan Fulaide coatings Co., Ltd, brand 1003F; the fluorinated polyurethane was purchased from Wuhan Fulaide coatings Co., Ltd, under the designation F909 type; the fluorosilicone varnish was purchased from Wuhan Fulaide coatings Co., Ltd, and was brand F808.
(4) Surface coating: spraying the coating solution on the surface of the aluminum alloy subjected to phosphoric acid anodic oxidation treatment at a constant speed under 0.4MPa by using a spray gun, wherein the distance between the spray gun and the surface of the aluminum alloy workpiece is 25 cm; after the spraying is finished, the thickness of the coating is about 37 mu m, and the coating is solidified for 24 hours at room temperature to obtain the super-hydrophobic composite coating on the surface of the aluminum alloy.
Under the preparation process conditions, the static contact angle of the prepared aluminum alloy surface super-hydrophobic composite coating is 148 degrees, and the rolling angle is 12 degrees. The preparation process does not carry out phosphoric acid anodic oxidation treatment on the aluminum alloy, the preparation process conditions of other coatings are the same as those in the example 3, and obviously, compared with the coating prepared on the surface of the aluminum alloy subjected to phosphoric acid anodic oxidation treatment in the example 3, the hydrophobic property of the coating prepared in the comparative example is obviously lower.
Within the value range of the invention, the corresponding components and process parameters have limited influence on the hydrophobic performance of the super-hydrophobic composite coating on the surface of the aluminum alloy.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A preparation method of a super-hydrophobic composite coating on the surface of an aluminum alloy is characterized by comprising the following steps: after phosphoric acid anodic oxidation treatment is carried out on the surface of the aluminum alloy, nano silicon dioxide subjected to hydrophobic modification is adopted as one of the components of the coating, and the super-hydrophobic composite coating is prepared by spraying on the surface of the aluminum alloy.
2. The preparation method of the superhydrophobic composite coating on the surface of the aluminum alloy according to claim 1, wherein the preparation method comprises the following steps: the method specifically comprises the following steps:
step (1), cleaning the surface of the aluminum alloy: ultrasonically cleaning the surface of the aluminum alloy by using ethanol and deionized water in sequence to remove surface oil stains;
step (2), phosphoric acid anodic oxidation treatment of the surface of the aluminum alloy: firstly, preparing a phosphoric acid aqueous solution with the mass concentration of 10-14 wt.%; putting the solution into an anodic oxidation tank, putting an aluminum alloy part into an anode, electrifying a cathode by adopting stainless steel to carry out anodic oxidation treatment; after the treatment is finished, taking out the aluminum alloy part, and washing the aluminum alloy part by running water; then drying;
step (3), for SiO2Carrying out hydrophobic modification treatment: mixing nano SiO2Putting into ammonia water, and ultrasonically dispersing for 30min to obtain a mixed solution; mixing 1H,1H,2H, 2H-perfluorodecyl triethoxysilane (PFDTES) with ethanol, wherein the concentration of the PFDTES is 0.8-1.0 wt%, and stirring in a magnetic stirrer for 1H to obtain PFDTES ethanol mixed solution; then pouring the silicon dioxide ammonia water mixed solution into the PFDTES ethanol mixed solution, and fully stirring in a magnetic stirrer; then placing the mixture into a centrifuge for centrifugal treatment; the centrifuged SiO2Putting the colloid into a vacuum drying oven for drying;
step (4), surface coating and preparing a composite coating: with hydrophobically modified SiO2Ethyl acetate, epoxy resin, fluorine-containing polyurethane, fluorine-containing silicon varnish and isophorone diamine are used as raw materials to prepare a coating; ultrasonically dispersing for 30min to mix uniformly; spraying the coating on the surface of the aluminum alloy subjected to phosphoric acid anodic oxidation treatment at a constant speed under 0.4MPa by using a spray gun; after the spraying was completed, it was allowed to stand at room temperatureAnd curing for 24 hours to obtain the super-hydrophobic composite coating on the surface of the aluminum alloy.
3. The preparation method of the superhydrophobic composite coating on the surface of the aluminum alloy according to claim 2, wherein the preparation method comprises the following steps: in the step (2), the voltage of phosphoric acid anodic oxidation treatment is 10-12V, and the time is 20-25 min.
4. The preparation method of the superhydrophobic composite coating on the surface of the aluminum alloy according to claim 2, wherein the preparation method comprises the following steps: in the step (3), the concentration of ammonia water is 5-6 wt%; nano SiO2The mass ratio of the ammonia water to the ammonia water is 1:6 to 1: 8.
5. The preparation method of the superhydrophobic composite coating on the surface of the aluminum alloy according to claim 2, wherein the preparation method comprises the following steps: in the step (3), the silica ammonia water mixed solution is poured into the PFDTES ethanol mixed solution, and the mass ratio of the silica ammonia water mixed solution to the PFDTES ethanol mixed solution is 1:3.2 to 1: 3.8.
6. The preparation method of the superhydrophobic composite coating on the surface of the aluminum alloy according to claim 2, wherein the preparation method comprises the following steps: in the step (3), the stirring time in the magnetic stirrer is 20-30h, and the temperature is 40-50 ℃.
7. The preparation method of the superhydrophobic composite coating on the surface of the aluminum alloy according to claim 2, wherein the preparation method comprises the following steps: in the step (3), when the centrifuge is used for centrifugal treatment, the rotation speed of the centrifuge is 4000-.
8. The preparation method of the superhydrophobic composite coating on the surface of the aluminum alloy according to claim 2, wherein the preparation method comprises the following steps: in the step (3), the vacuum drying time is 10-15h, and the temperature is 60-70 ℃.
9. The aluminum alloy surface super-hydrophobic material as claimed in claim 2The preparation method of the composite coating is characterized by comprising the following steps: in the step (4), the paint comprises the following raw materials in parts by weight: modified SiO21.5 to 2.5 percent of ethyl acetate, 1.5 to 2.5 percent of epoxy resin, 0.4 to 0.8 percent of fluorine-containing polyurethane, 1.2 to 2.0 percent of fluorine-silicon varnish and 0.6 to 1.0 percent of isophorone diamine.
10. The preparation method of the superhydrophobic composite coating on the surface of the aluminum alloy according to claim 2, wherein the preparation method comprises the following steps: in the step (4), the used epoxy resin is purchased from Wuhan Fulaide paint Co., Ltd, and is of a brand 1003F type; the fluorinated polyurethane was purchased from Wuhan Fulaide coatings Co., Ltd, under the designation F909 type; the fluorosilicone varnish was purchased from Wuhan Fulaide coatings Co., Ltd, and was brand F808.
CN202010695661.6A 2020-07-20 2020-07-20 Preparation method of super-hydrophobic composite coating on surface of aluminum alloy Pending CN111822296A (en)

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CN112979175A (en) * 2021-02-07 2021-06-18 兰州理工大学科技园有限公司 Hydrophobic and oleophobic coating and preparation method thereof
CN113737246A (en) * 2021-11-08 2021-12-03 山东裕航特种合金装备有限公司 Micro-arc oxidation treatment process for aluminum alloy surface
CN114292426A (en) * 2021-12-01 2022-04-08 湖南科技大学 Preparation method of super-hydrophobic porous aluminum alloy-epoxy resin anticorrosive composite material
CN114985236A (en) * 2022-07-14 2022-09-02 国网福建省电力有限公司电力科学研究院 Preparation method of super-hydrophobic antifouling coating on surface of glass insulator
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
CN115805183A (en) * 2022-11-01 2023-03-17 佛山泰铝新材料有限公司 Production method of curtain wall aluminum plate oxidation coating film

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CN109746172A (en) * 2019-01-29 2019-05-14 南京航空航天大学 A kind of preparation method of the ice-covering-proof/anticorrosion integrated function super-hydrophobic coat of aviation

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CN109746172A (en) * 2019-01-29 2019-05-14 南京航空航天大学 A kind of preparation method of the ice-covering-proof/anticorrosion integrated function super-hydrophobic coat of aviation

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CN112979175A (en) * 2021-02-07 2021-06-18 兰州理工大学科技园有限公司 Hydrophobic and oleophobic coating and preparation method thereof
CN113737246A (en) * 2021-11-08 2021-12-03 山东裕航特种合金装备有限公司 Micro-arc oxidation treatment process for aluminum alloy surface
CN114292426A (en) * 2021-12-01 2022-04-08 湖南科技大学 Preparation method of super-hydrophobic porous aluminum alloy-epoxy resin anticorrosive composite material
CN114292426B (en) * 2021-12-01 2023-02-28 湖南科技大学 Preparation method of super-hydrophobic porous aluminum alloy-epoxy resin anticorrosive composite material
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
CN114985236A (en) * 2022-07-14 2022-09-02 国网福建省电力有限公司电力科学研究院 Preparation method of super-hydrophobic antifouling coating on surface of glass insulator
CN114985236B (en) * 2022-07-14 2023-09-19 国网福建省电力有限公司电力科学研究院 Preparation method of super-hydrophobic antifouling coating on surface of glass insulator
CN115805183A (en) * 2022-11-01 2023-03-17 佛山泰铝新材料有限公司 Production method of curtain wall aluminum plate oxidation coating film

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Application publication date: 20201027