CN117186710A - Self-repairing anti-corrosion composite coating and preparation method thereof - Google Patents
Self-repairing anti-corrosion composite coating and preparation method thereof Download PDFInfo
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- 239000011248 coating agent Substances 0.000 title claims abstract description 230
- 238000005260 corrosion Methods 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 claims abstract description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910000733 Li alloy Inorganic materials 0.000 claims abstract description 54
- 239000001989 lithium alloy Substances 0.000 claims abstract description 54
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 claims abstract description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000001263 FEMA 3042 Substances 0.000 claims abstract description 42
- 229920002258 tannic acid Polymers 0.000 claims abstract description 42
- 229940033123 tannic acid Drugs 0.000 claims abstract description 42
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims abstract description 39
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims abstract description 39
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims abstract description 39
- 235000015523 tannic acid Nutrition 0.000 claims abstract description 39
- 239000003822 epoxy resin Substances 0.000 claims abstract description 28
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 28
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 26
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000003973 paint Substances 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 20
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 15
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- 238000007254 oxidation reaction Methods 0.000 claims description 14
- 239000004115 Sodium Silicate Substances 0.000 claims description 9
- 239000011698 potassium fluoride Substances 0.000 claims description 9
- 235000003270 potassium fluoride Nutrition 0.000 claims description 9
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 3
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- 239000001257 hydrogen Substances 0.000 abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 14
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- 238000006243 chemical reaction Methods 0.000 abstract 1
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 21
- 229910010271 silicon carbide Inorganic materials 0.000 description 21
- 238000001035 drying Methods 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 12
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
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- 239000010410 layer Substances 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
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- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 230000003993 interaction Effects 0.000 description 5
- 229910001425 magnesium ion Inorganic materials 0.000 description 5
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- 230000008901 benefit Effects 0.000 description 4
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000010981 drying operation Methods 0.000 description 4
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
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- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention provides a preparation method of a self-repairing anti-corrosion composite coating, which comprises the following steps: preparing a micro-arc oxidation coating on the surface of the magnesium-lithium alloy; mixing polyvinyl alcohol, tannic acid, ethanol and water to obtain self-repairing paint; coating the self-repairing coating on the surface of the micro-arc oxidation coating to obtain a self-repairing coating; and coating epoxy resin on the surface of the self-repairing coating to obtain the self-repairing anti-corrosion composite coating. The micro-arc oxidation coating is prepared on the surface of the magnesium-lithium alloy, so that the corrosion of a corrosive medium in a corrosive environment can be effectively resisted; the micro-arc oxidation coating with the micropore structure can provide pinning sites for the self-repairing coating, so that the micro-arc oxidation coating and the self-repairing coating form mechanical linkage, and the adhesive force of the coating is improved; by combining the complexing reaction of tannic acid molecules and the reversible effect of dynamic hydrogen bonds with the swelling action of the polymer, a triple self-repairing coating is constructed, the protective capability of the magnesium-lithium alloy material can be greatly improved, and the service life of the magnesium-lithium alloy can be prolonged.
Description
Technical Field
The invention relates to the technical field of metal surface treatment, in particular to a self-repairing anti-corrosion composite coating and a preparation method thereof.
Background
The magnesium-lithium alloy is the lightest metal structural material at present, has the advantages of high specific stiffness, high impact toughness, good electromagnetic shielding performance and the like of common magnesium alloy, has the advantages of low density, easy processing and the like, is a light-weight preferred material in the fields of communication electronics, automobiles, aerospace, national defense and the like, and is known as a green metal engineering material in the 21 st century. However, since magnesium and lithium belong to active metal elements and have lower standard potential, magnesium-lithium alloy is easy to corrode in corrosive medium, and oxide generated after corrosion of magnesium-lithium alloy is loose and porous, so that invasion of corrosive medium cannot be prevented. The low corrosion resistance of the magnesium-lithium alloy severely limits the large-scale engineering application of the magnesium-lithium alloy, so that the improvement of the corrosion resistance of the magnesium-lithium alloy becomes a technical problem which needs to be solved in the field of engineering application.
The construction of a dense and stable physical barrier is an economical and effective way to reduce the contact of the corrosive medium with the magnesium-lithium alloy matrix and further inhibit the corrosion of the magnesium-lithium alloy. Micro-arc oxidation coatings are widely used for corrosion and protection of magnesium-lithium alloys with their excellent corrosion and wear resistance. Although the micro-arc oxidation coating has various excellent physical and chemical properties (such as abrasion resistance, corrosion resistance and the like), a large number of micropores and microcrack defects are formed on the surface of the substrate due to continuous and strong spark and gas precipitation on the surface of the substrate in the preparation process of the coating, and aggressive solution can infiltrate into the defects, so that the corrosion resistance of the substrate is seriously damaged. Meanwhile, the coating is inevitably mechanically damaged during service, so that the substrate is exposed to corrosive environment, and the service life of the coating is reduced. Therefore, developing a coating with excellent corrosion resistance is a technical problem to be solved in the art.
Disclosure of Invention
The invention aims to provide a self-repairing anti-corrosion composite coating and a preparation method thereof. The self-repairing anti-corrosion composite coating prepared by the preparation method provided by the invention can greatly improve the protective capability of the magnesium-lithium alloy and prolong the service life of the magnesium-lithium alloy.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a self-repairing anti-corrosion composite coating, which comprises the following steps:
(1) Preparing a micro-arc oxidation coating on the surface of the magnesium-lithium alloy;
(2) Mixing polyvinyl alcohol, tannic acid, ethanol and water to obtain self-repairing paint;
(3) Coating the self-repairing coating obtained in the step (2) on the surface of the micro-arc oxidation coating obtained in the step (1) to obtain the self-repairing coating;
(4) Coating epoxy resin on the surface of the self-repairing coating obtained in the step (3) to obtain a self-repairing anti-corrosion composite coating;
the step (1) and the step (2) are not in sequence.
Preferably, the electrolyte used for preparing the micro-arc oxidation coating in the step (1) is 7.5-8.5 g/L of sodium hydroxide, 9.5-10.5 g/L of sodium silicate, 4.5-5.5 g/L of potassium fluoride and water.
Preferably, the electrolyte used for preparing the micro-arc oxidation coating is 8g/L of sodium hydroxide, 10g/L of sodium silicate, 5g/L of potassium fluoride and water.
Preferably, the process parameters for preparing the micro-arc oxidation coating in the step (1) include: alternating current is 250-400V, pulse frequency is 400-500 Hz, oxidation time is 3-5 min, and oxidation temperature is 30-42 ℃.
Preferably, the thickness of the micro-arc oxidation coating in the step (1) is 10-17 μm.
Preferably, the mass ratio of polyvinyl alcohol to tannic acid in the step (2) is 1: (1.2-2), wherein the volume ratio of the ethanol to the water is (0.3-0.9): 1.
preferably, the mixing in step (2) is performed under stirring.
Preferably, the stirring speed is 200-300 r/min, the stirring time is 1-1.5 h, and the stirring temperature is more than 90 ℃.
Preferably, the thickness of the self-repairing coating in the step (3) is 7-15 μm.
Preferably, the thickness of the epoxy resin in the step (4) is 6 to 8 μm.
The invention also provides the self-repairing anti-corrosion composite coating prepared by the preparation method.
The invention provides a preparation method of a self-repairing anti-corrosion composite coating, which comprises the following steps: preparing a micro-arc oxidation coating on the surface of the magnesium-lithium alloy; mixing polyvinyl alcohol, tannic acid, ethanol and water to obtain self-repairing paint; coating the self-repairing coating on the surface of the micro-arc oxidation coating to obtain a self-repairing coating; and coating epoxy resin on the surface of the self-repairing coating to obtain the self-repairing anti-corrosion composite coating. Firstly, preparing a micro-arc oxidation coating on the surface of the magnesium-lithium alloy, so that the corrosion of a corrosive medium in a corrosive environment can be effectively resisted; meanwhile, the micro-arc oxidation coating with the micropore structure can provide pinning sites for the self-repairing coating, so that the micro-arc oxidation coating and the self-repairing coating form mechanical linkage, and the adhesive force of the coating is further improved; the crosslinked polymer network with the self-healing function is prepared on the surface of the ceramic layer by utilizing the hydrogen bond reversible characteristic between polyvinyl alcohol and tannic acid, has dynamic reversible characteristic when meeting water, and can repair the coating through the hydrogen bond action after the coating is damaged, which is the first self-repairing action; the self-repairing coating at the damaged part swells when meeting water by utilizing the water swelling characteristic of the self-repairing coating, so that the damaged part of the epoxy coating layer is quickly filled, the self-healing of the epoxy coating layer is realized, and the self-repairing effect is a second self-repairing effect; the tannic acid molecules in the self-repairing coating can be further complexed with magnesium ions at the damaged part of the coating to generate tannic acid magnesium, the tannic acid magnesium is deposited at the damaged part of the coating, the coating is further healed, and the service life of the coating is prolonged. Experimental results show that compared with a bare substrate, the self-repairing anti-corrosion composite coating prepared by the preparation method provided by the invention has the advantages that the modulus can be improved by eight orders of magnitude, and the coating has excellent anti-corrosion performance.
Drawings
FIG. 1 is a schematic illustration of the preparation of a self-healing corrosion-resistant composite coating provided by the invention;
FIG. 2 is a schematic diagram of three self-repairing mechanisms of the self-repairing anticorrosive composite coating provided by the invention;
FIG. 3 is an electron microscope image of the self-repairing anticorrosive composite coating prepared in example 1 before being soaked in water;
FIG. 4 is an electron microscope image of the self-repairing anticorrosive composite coating prepared in example 1 after being soaked in water;
FIG. 5 is the electrochemical impedance spectrum model data of the magnesium-lithium alloy, micro-arc oxidation coating, self-healing coating, and self-healing corrosion-resistant composite coating of example 1;
FIG. 6 is the electrochemical impedance spectrum model data of the magnesium-lithium alloy, micro-arc oxidation coating, self-healing coating, and self-healing corrosion-resistant composite coating of example 2;
FIG. 7 is the electrochemical impedance spectrum model data of the magnesium-lithium alloy, micro-arc oxidation coating, self-healing coating, and self-healing corrosion-resistant composite coating of example 3;
in fig. 5 to 7, 1 is a magnesium-lithium alloy, 2 is a micro-arc oxidation coating, 3 is a self-repairing coating, and 4 is a self-repairing corrosion-resistant composite coating.
Detailed Description
The invention provides a preparation method of a self-repairing anti-corrosion composite coating, which comprises the following steps:
(1) Preparing a micro-arc oxidation coating on the surface of the magnesium-lithium alloy;
(2) Mixing polyvinyl alcohol, tannic acid, ethanol and water to obtain self-repairing paint;
(3) Coating the self-repairing coating obtained in the step (2) on the surface of the micro-arc oxidation coating obtained in the step (1) to obtain the self-repairing coating;
(4) Coating epoxy resin on the surface of the self-repairing coating obtained in the step (3) to obtain a self-repairing anti-corrosion composite coating;
the step (1) and the step (2) are not in sequence.
The invention prepares the micro-arc oxidation coating on the surface of the magnesium-lithium alloy. The micro-arc oxidation coating is prepared on the surface of the magnesium-lithium alloy, so that the corrosion of a corrosive medium in a corrosive environment can be effectively resisted; meanwhile, the micro-arc oxidation coating with the micropore structure can provide pinning sites for the self-repairing coating, so that the micro-arc oxidation coating and the self-repairing coating form mechanical linkage, and the adhesive force of the coating is further improved.
The source of the magnesium-lithium alloy is not particularly limited, and the magnesium-lithium alloy is prepared by a preparation method well known to those skilled in the art.
In the invention, the magnesium-lithium alloy is preferably pretreated before use; the pretreatment is preferably polishing, washing and drying which are sequentially performed. According to the invention, the stains on the surface of the magnesium-lithium alloy can be removed by pretreatment of the magnesium-lithium alloy.
In the present invention, the polishing is preferably performed by using 100# silicon carbide abrasive paper, 400# silicon carbide abrasive paper, 800# silicon carbide abrasive paper, 1500# silicon carbide abrasive paper and 2000# silicon carbide abrasive paper. The present invention is not particularly limited to the polishing operation using 100#,400#,800#,1500# and 2000# silicon carbide abrasive papers in this order, and polishing operations well known to those skilled in the art may be used.
In the present invention, the washing is preferably washing with distilled water and alcohol in this order. The present invention is not particularly limited to the above-described washing operation using distilled water and alcohol in this order, and may be carried out using an operation well known to those skilled in the art.
The drying operation is not particularly limited, and may be performed by any operation known to those skilled in the art.
In the invention, the electrolyte used for preparing the micro-arc oxidation coating is preferably 7.5-8.5 g/L of sodium hydroxide, 9.5-10.5 g/L of sodium silicate, 4.5-5.5 g/L of potassium fluoride and water, more preferably 8g/L of sodium hydroxide, 10g/L of sodium silicate, 5g/L of potassium fluoride and water. The method for preparing the electrolyte is not particularly limited, and the electrolyte can be prepared by a preparation method well known to those skilled in the art. The invention can control the micro-arc oxidation coating by controlling the composition of the electrolyte to obtain the wear-resistant microporous ceramic layer, which mainly comprises magnesium oxide, magnesium silicate and magnesium fluoride.
In the present invention, the process parameters for preparing the micro-arc oxidation coating preferably include: alternating current is 250-400V, pulse frequency is 400-500 Hz, oxidation time is 3-5 min, and oxidation temperature is 30-42 ℃; more preferably: alternating current 300V, pulse frequency 500Hz, oxidation time 4-5 min, oxidation temperature 35-40 ℃. The invention can ensure the film forming quality of the micro-arc oxidation coating by controlling the technological parameters for preparing the micro-arc oxidation coating.
In the present invention, the thickness of the micro-arc oxidation coating is preferably 10 to 17 μm.
After the micro-arc oxidation coating is prepared, the method preferably further comprises the steps of sequentially cleaning and drying the micro-arc oxidation coating.
In the present invention, the washing is preferably washing with distilled water and alcohol in this order. The present invention is not particularly limited to the above-described washing operation using distilled water and alcohol in this order, and may be carried out using an operation well known to those skilled in the art.
The drying operation is not particularly limited, and may be performed by any operation known to those skilled in the art.
The self-repairing paint is prepared by mixing polyvinyl alcohol, tannic acid, ethanol and water. In the invention, water is used as a solvent of tannic acid and polyvinyl alcohol, but the tannic acid and the polyvinyl alcohol under the water solution have strong hydrogen bond interaction, so that precipitation can be caused, the ethanol can weaken the strong hydrogen bond interaction between the tannic acid and the polyvinyl alcohol, and meanwhile, the viscosity of the tannic acid and the polyvinyl alcohol is improved.
In the present invention, the water is preferably deionized water.
In the present invention, the operation of mixing the polyvinyl alcohol, tannic acid, ethanol and water is preferably: mixing ethanol and water, adding polyvinyl alcohol and tannic acid, and mixing.
In the present invention, the mass ratio of the polyvinyl alcohol to the tannic acid is preferably 1: (1.2 to 2), more preferably 1: (1.25-1.5); the volume ratio of the ethanol to the water is preferably (0.3-0.9): 1, more preferably (0.6 to 0.8): 1, a step of; the volume ratio of the tannic acid substance to water is preferably (0.05 to 0.3) mol:1L, more preferably (0.08 to 0.13) mol:1L. The invention can further improve the self-repairing effect of the self-repairing coating by controlling the proportion relation of the raw materials.
The invention is not particularly limited to the mixing of ethanol and water, and the technical scheme for preparing the mixture is well known to those skilled in the art.
In the present invention, the operation of adding the polyvinyl alcohol and tannic acid to be mixed is preferably performed under stirring; the rotation speed of stirring is preferably 200-300 r/min; the stirring time is preferably 1 to 1.5 hours; the temperature of the stirring is preferably > 90 ℃, more preferably 100 ℃.
After the micro-arc oxidation coating and the self-repairing coating are obtained, the self-repairing coating is coated on the surface of the micro-arc oxidation coating to obtain the self-repairing coating. The hydroxyl groups in the polyvinyl alcohol and the phenolic hydroxyl groups in the tannic acid can be combined together through a plurality of intermolecular hydrogen bonds, when the polymer is damaged and meets water, partial polymer meets water to form free polymer, the free polymer and the non-free polymer are combined together again through the hydrogen bond interaction between the hydroxyl groups and the phenolic hydroxyl groups, a crosslinked polymer network with a self-healing function is prepared on the surface of the ceramic layer by utilizing the reversible characteristic of the hydrogen bond between the polyvinyl alcohol and the tannic acid, and the crosslinked polymer network has the dynamic reversible characteristic when meeting water, can repair the coating through the hydrogen bond action after the coating is damaged, and is the first self-repairing function; the self-repairing coating at the damaged part swells when meeting water by utilizing the water swelling characteristic of the self-repairing coating, so that the damaged part of the epoxy coating layer is quickly filled, the self-healing of the epoxy coating layer is realized, and the self-repairing effect is a second self-repairing effect; the tannic acid molecules in the self-repairing coating can be further complexed with magnesium ions at the damaged part of the coating to generate tannic acid magnesium, the tannic acid magnesium is deposited at the damaged part of the coating, the coating is further healed, and the service life of the coating is prolonged.
In the present invention, the self-repairing coating is preferably applied to the surface of the micro-arc oxidation coating by dropping the self-repairing coating onto the surface of the micro-arc oxidation coating, and then spin coating or dipping the micro-arc oxidation coating into the self-repairing coating.
The self-repairing coating is preferably dripped on the surface of the micro-arc oxidation coating, and then spin coating is carried out to obtain the self-repairing coating.
The dripping operation is not particularly limited, and may be performed by any operation known to those skilled in the art. The invention is not particularly limited in the amount to be added, and the thickness of the self-repairing coating is adjusted according to the requirement.
In the invention, the spin coating is preferably performed by a spin coater; the rotating speed of the spin coater is preferably 800-1000 r/min. The type of the spin coater is not particularly limited, and the spin coater may be any one known to those skilled in the art.
After spin coating is completed, the self-repairing coating is preferably obtained by drying a product obtained by spin coating. The drying operation is not particularly limited, and may be performed by those known to those skilled in the art.
The micro-arc oxidation coating is preferably soaked in the self-repairing coating to obtain the self-repairing coating.
In the present invention, the soaking time is preferably 2s to 2min, more preferably 1min.
After the soaking is finished, the self-repairing coating is preferably obtained by drying the soaked product. The drying operation is not particularly limited, and may be performed by those known to those skilled in the art.
In the present invention, the thickness of the self-repairing coating is preferably 7 to 15 μm.
After the self-repairing coating is obtained, the surface of the self-repairing coating is coated with epoxy resin, so that the self-repairing anti-corrosion composite coating is obtained. The epoxy resin of the invention is used as an outer shell layer and has two main functions, namely, the epoxy resin is used as a physical barrier layer to inhibit aggressive ions and aqueous solution from entering the self-repairing coating; secondly, the polyurethane is used as an outer barrier layer to reduce the diffusion effect of the tannic acid polyvinyl alcohol polymer in the aqueous solution.
In the invention, the epoxy resin is preferably prepared by mixing a main agent of the Kavut epoxy resin A and a curing agent of the Kavut epoxy resin B; the mass ratio of the main agent of the carbofuran epoxy resin A to the curing agent of the carbofuran epoxy resin B is preferably 2:1.
the operation of mixing the main agent of the carbofuran epoxy resin A and the curing agent of the carbofuran epoxy resin B is not particularly limited, and the mixing operation well known to those skilled in the art can be adopted.
In the present invention, the coating is preferably spray gun coating. The spraying operation by the spray gun is not particularly limited, and may be performed by those known to those skilled in the art.
In the present invention, the thickness of the epoxy resin is preferably 6 to 8 μm.
The sources of the above raw materials are not particularly limited, and commercially available products known to those skilled in the art may be used.
According to the invention, a three-layer hybrid self-repairing coating is formed on the surface of the magnesium-lithium alloy, and the triple self-repairing effect of the coating is realized through the complexation reaction of tannic acid molecules and magnesium ions, the dynamic hydrogen bond reversible effect of tannic acid polyvinyl alcohol and the swelling effect of the polymer, so that the self-repairing capability and the corrosion resistance of the magnesium-lithium alloy can be greatly improved, and the service life of the magnesium-lithium alloy is prolonged.
The self-repairing coating of the self-repairing anticorrosive composite coating is assembled together through hydrogen bonds, has dynamic reversible characteristics when meeting water, and can quickly repair scratches; the self-repairing coating at the damaged part swells when meeting water, so that the damaged part of the epoxy coating layer is quickly filled, the self-healing of the epoxy coating is realized, and meanwhile, tannic acid molecules in the self-repairing coating can be further complexed with magnesium ions at the damaged part of the coating, and deposited at the damaged part of the coating, the healing of the coating is further realized, and the service life of the coating is prolonged.
The preparation schematic diagram of the self-repairing anti-corrosion composite coating provided by the invention is shown in figure 1. As can be seen from fig. 1, firstly, a micro-arc oxidation method is adopted to prepare a micro-arc oxidation coating on the surface of a magnesium-lithium alloy, then a self-repair coating (polyvinyl alcohol-tannic acid self-repair coating) is prepared, and then epoxy resin is sprayed on the surface of the self-repair coating, so that the self-repair corrosion-resistant composite coating is obtained.
The three self-repairing mechanism schematic diagrams of the self-repairing anticorrosive composite coating provided by the invention are shown in figure 2. As can be seen from fig. 2, healing mechanism 1: the hydroxyl groups in the polyvinyl alcohol and the phenolic hydroxyl groups in the tannic acid can be combined together through a plurality of intermolecular hydrogen bonds, when the polymer is damaged and meets water, part of the polymer meets water to form free polymers, and the free polymers and the non-free polymers are combined together again through the hydrogen bond interaction between the hydroxyl groups and the phenolic hydroxyl groups; healing mechanism 2: the polyvinyl alcohol-tannic acid self-repairing coating swells when meeting water, so that the damaged part of the epoxy coating shell is quickly filled, and the self-healing of the epoxy coating shell is realized; healing mechanism 3: the tannic acid molecules of the polyvinyl alcohol-tannic acid self-repairing coating can be further complexed with magnesium ions at the damaged part of the coating to generate tannic acid magnesium, the tannic acid magnesium is deposited at the damaged part of the coating, and the surface of a substrate is prevented from being corroded by corrosive ions, so that the healing of the damaged part is realized.
The invention also provides the self-repairing anti-corrosion composite coating prepared by the preparation method.
The self-repairing anti-corrosion composite coating provided by the invention has excellent anti-corrosion performance and long service life.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the LA81 magnesium-lithium alloy self-repairing anti-corrosion composite coating comprises the following steps:
(1) Sequentially polishing LA81 magnesium-lithium alloy by using 100# silicon carbide abrasive paper, 400# silicon carbide abrasive paper, 800# silicon carbide abrasive paper, 1500# silicon carbide abrasive paper and 2000# silicon carbide abrasive paper, sequentially cleaning the surface of the LA81 magnesium-lithium alloy by using distilled water and alcohol, drying the LA81 magnesium-lithium alloy in a 60 ℃ oven, and preparing a micro-arc oxidation coating on the surface of the LA81 magnesium-lithium alloy by adopting a micro-arc oxidation method; wherein, 8g/L of sodium hydroxide, 10g/L of sodium silicate, 5g/L of potassium fluoride and water are adopted for preparing the micro-arc oxidation coating, the technological parameters of the micro-arc oxidation method are 300V alternating current, the pulse frequency is 500Hz, the oxidation time is 5min, the oxidation temperature is 35 ℃, distilled water and alcohol are sequentially used for cleaning, and the micro-arc oxidation coating with the thickness of 17 mu m is obtained by drying in a 60 ℃ oven;
(2) 5g of tannic acid and 4g of polyvinyl alcohol are added into a mixed solution containing 30mL of ethanol and 35mL of deionized water, and then the mixed solution is mechanically stirred for 80min at the temperature of 100 ℃ to obtain self-repairing paint; wherein the stirring speed is 300r/min;
(3) Soaking the micro-arc oxidation coating obtained in the step (1) into the self-repairing coating obtained in the step (2) for 1min, then taking out, placing in a 70 ℃ oven, and drying for 30min to obtain a self-repairing coating with the thickness of 10 mu m;
(4) The main agent of the Kavut epoxy resin A and the curing agent of the Kavut epoxy resin B are mixed according to the mass ratio of 2:1, mixing and stirring uniformly, and spraying the mixture on the surface of the self-repairing coating obtained in the step (3) through a spray gun to form epoxy resin with the thickness of 6 mu m, thereby obtaining the self-repairing anti-corrosion composite coating.
Example 2
The preparation method of the LA81 magnesium-lithium alloy self-repairing anti-corrosion composite coating comprises the following steps:
(1) Sequentially polishing LA81 magnesium-lithium alloy by using 100# silicon carbide abrasive paper, 400# silicon carbide abrasive paper, 800# silicon carbide abrasive paper, 1500# silicon carbide abrasive paper and 2000# silicon carbide abrasive paper, sequentially cleaning the surface of the LA81 magnesium-lithium alloy by using distilled water and alcohol, drying the LA81 magnesium-lithium alloy in a 60 ℃ oven, and preparing a micro-arc oxidation coating on the surface of the LA81 magnesium-lithium alloy by adopting a micro-arc oxidation method; wherein, 8g/L of sodium hydroxide, 10g/L of sodium silicate, 5g/L of potassium fluoride and water are adopted for preparing the micro-arc oxidation coating, the technological parameters of the micro-arc oxidation method are 300V alternating current, the pulse frequency is 500Hz, the oxidation time is 5min, the oxidation temperature is 35 ℃, distilled water and alcohol are sequentially used for cleaning, and the micro-arc oxidation coating with the thickness of 17 mu m is obtained by drying in a 60 ℃ oven;
(2) 5g of tannic acid and 4g of polyvinyl alcohol are added into a mixed solution containing 30mL of ethanol and 35mL of deionized water, and then the mixed solution is mechanically stirred for 80min at the temperature of 100 ℃ to obtain self-repairing paint; wherein the stirring speed is 300r/min;
(3) 1mL of the self-repairing coating obtained in the step (2) is dripped on the surface of the micro-arc oxidation coating obtained in the step (1), spin-coating is carried out for a plurality of times by a spin coater, and then the self-repairing coating is taken out and placed in a 70 ℃ oven for drying for 30min, so that the self-repairing coating with the thickness of 7 mu m is obtained; wherein the rotating speed of the spin coater is 800r/min;
(4) The main agent of the Kavut epoxy resin A and the curing agent of the Kavut epoxy resin B are mixed according to the mass ratio of 2:1, mixing and stirring uniformly, and spraying the mixture on the surface of the self-repairing coating obtained in the step (3) through a spray gun to form epoxy resin with the thickness of 6 mu m, thereby obtaining the self-repairing anti-corrosion composite coating.
Example 3
The preparation method of the LA81 magnesium-lithium alloy self-repairing anti-corrosion composite coating comprises the following steps:
(1) Sequentially polishing LA81 magnesium-lithium alloy by using 100# silicon carbide abrasive paper, 400# silicon carbide abrasive paper, 800# silicon carbide abrasive paper, 1500# silicon carbide abrasive paper and 2000# silicon carbide abrasive paper, sequentially cleaning the surface of the LA81 magnesium-lithium alloy by using distilled water and alcohol, drying the LA81 magnesium-lithium alloy in a 60 ℃ oven, and preparing a micro-arc oxidation coating on the surface of the LA81 magnesium-lithium alloy by adopting a micro-arc oxidation method; wherein, 8g/L of sodium hydroxide, 10g/L of sodium silicate, 5g/L of potassium fluoride and water are adopted for preparing the micro-arc oxidation coating, the technological parameters of the micro-arc oxidation method are 300V alternating current, the pulse frequency is 500Hz, the oxidation time is 5min, the oxidation temperature is 35 ℃, distilled water and alcohol are sequentially used for cleaning, and the micro-arc oxidation coating with the thickness of 17 mu m is obtained by drying in a 60 ℃ oven;
(2) 8g of tannic acid and 4g of polyvinyl alcohol are added into a mixed solution containing 11mL of ethanol and 35mL of deionized water, and then the mixed solution is mechanically stirred for 80min at the temperature of 100 ℃ to obtain self-repairing paint; wherein the stirring speed is 200r/min;
(3) Soaking the micro-arc oxidation coating obtained in the step (1) into the self-repairing coating obtained in the step (2) for 1min, and then taking out, placing in a 70 ℃ oven, and drying for 30min to obtain the self-repairing coating with the thickness of 15 mu m;
(4) The main agent of the Kavut epoxy resin A and the curing agent of the Kavut epoxy resin B are mixed according to the mass ratio of 2:1, mixing and stirring uniformly, and spraying the mixture on the surface of the self-repairing coating obtained in the step (3) through a spray gun to form the epoxy resin with the thickness of 8 mu m, thereby obtaining the self-repairing anti-corrosion composite coating.
A scratch with the width of about 50 micrometers is prefabricated on the surface of the self-repairing anti-corrosion composite coating prepared in the embodiment 1 by using a surgical blade, the scratch depth penetrates through the whole composite coating, then a layer of water film is dripped on the surface of the coating for simulating an corrosion environment, the water film exists for 1h on the surface of the coating, and then the surface morphology of the scratch before and after soaking is recorded by using an electron microscope, wherein fig. 3 is an electron microscope diagram before the self-repairing anti-corrosion composite coating prepared in the embodiment 1 is soaked in water, and fig. 4 is an electron microscope diagram after the self-repairing anti-corrosion composite coating prepared in the embodiment 1 is soaked in water.
As can be seen from fig. 3 to 4, the self-repairing anticorrosive composite coating prepared by the present invention fills the damaged portion (damage caused by the scalpel) under the stimulation of the corrosive medium (aqueous solution), wherein the repair of the damaged portion (hydrogen bond interaction of hydroxyl groups and phenolic hydroxyl groups of tannic acid and polyvinyl alcohol polymers) can be clearly seen, and at the same time, the obvious swelling effect (swelling effect of the polymers when encountering water) can be seen at the damaged portion.
FIG. 5 is the electrochemical impedance spectrum model data of the magnesium-lithium alloy, micro-arc oxidation coating, self-healing coating, and self-healing corrosion-resistant composite coating of example 1; FIG. 6 is the electrochemical impedance spectrum model data of the magnesium-lithium alloy, micro-arc oxidation coating, self-healing coating, and self-healing corrosion-resistant composite coating of example 2; fig. 7 shows electrochemical impedance spectrum model data of the magnesium-lithium alloy, the micro-arc oxidation coating, the self-repairing coating and the self-repairing corrosion-resistant composite coating in example 3, and fig. 5 to 7 show that 1 is the magnesium-lithium alloy, 2 is the micro-arc oxidation coating, 3 is the self-repairing coating and 4 is the self-repairing corrosion-resistant composite coating.
From fig. 5 to 7, the self-repairing anti-corrosion composite coating prepared by the invention has the advantages of maximum modulus, best anti-corrosion performance, eight orders of magnitude improvement compared with a bare substrate, and excellent anti-corrosion performance.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A preparation method of a self-repairing anti-corrosion composite coating comprises the following steps:
(1) Preparing a micro-arc oxidation coating on the surface of the magnesium-lithium alloy;
(2) Mixing polyvinyl alcohol, tannic acid, ethanol and water to obtain self-repairing paint;
(3) Coating the self-repairing coating obtained in the step (2) on the surface of the micro-arc oxidation coating obtained in the step (1) to obtain the self-repairing coating;
(4) Coating epoxy resin on the surface of the self-repairing coating obtained in the step (3) to obtain a self-repairing anti-corrosion composite coating;
the step (1) and the step (2) are not in sequence.
2. The method according to claim 1, wherein the electrolyte used for preparing the micro-arc oxidation coating in the step (1) is 7.5-8.5 g/L of sodium hydroxide, 9.5-10.5 g/L of sodium silicate, 4.5-5.5 g/L of potassium fluoride and water.
3. The method according to claim 2, wherein the electrolyte used for preparing the micro-arc oxidation coating is 8g/L of sodium hydroxide, 10g/L of sodium silicate, 5g/L of potassium fluoride and water.
4. The method of claim 1, wherein the process parameters for preparing the micro-arc oxidation coating in step (1) include: alternating current is 250-400V, pulse frequency is 400-500 Hz, oxidation time is 3-5 min, and oxidation temperature is 30-42 ℃.
5. The method according to claim 1, wherein the micro-arc oxidation coating in the step (1) has a thickness of 10 to 17 μm.
6. The method according to claim 1, wherein the mass ratio of polyvinyl alcohol to tannic acid in the step (2) is 1: (1.2-2), wherein the volume ratio of the ethanol to the water is (0.3-0.9): 1.
7. the method according to claim 1, wherein the mixing in the step (2) is performed under stirring.
8. The method according to claim 1, wherein the self-repairing coating in the step (3) has a thickness of 7 to 15 μm.
9. The method according to claim 1, wherein the thickness of the epoxy resin in the step (4) is 6 to 8. Mu.m.
10. The self-repairing anticorrosive composite coating prepared by the preparation method of any one of claims 1 to 9.
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