CN109825866B - Preparation method of alloy self-repairing corrosion-resistant micro-arc oxidation coating - Google Patents
Preparation method of alloy self-repairing corrosion-resistant micro-arc oxidation coating Download PDFInfo
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Abstract
The invention belongs to the technical field of surface chemical treatment of metal materials, and particularly relates to a preparation method of an alloy self-repairing corrosion-resistant micro-arc oxidation coating. Firstly, a layer of micro-arc oxidation coating is formed on the surface of metal in silicate electrolyte by using pulse current, and then hole sealing post-treatment is carried out in phosphating solution containing corrosion inhibitor. In the process of preparing the micro-arc oxidation in-situ coating, the electrolyte comprises the following components: 10-80 g/L of sodium silicate, 1-10 g/L of potassium fluoride, 0.5-8 g/L of sodium hydroxide, 10-80 mL/L of ethylene glycol and the balance of water. The post-treatment solution consists of: 20-60 g/L of dihydric phosphate, 1-8 g/L of sodium nitrate, 10-50 g/L of corrosion inhibitor, 20-60 g/L, EDTA g/L of sulfate tetrasodium, and the balance of water. The invention can solve the defects of high micro-arc oxidation void ratio and poor corrosion resistance caused by easy invasion of corrosive medium into the matrix at present.
Description
Technical Field
The invention belongs to the technical field of surface chemical treatment of metal materials, and particularly relates to a preparation method of an alloy self-repairing corrosion-resistant micro-arc oxidation coating.
Background
With the development of socio-economy, the role of metal and alloy materials in production and life is more and more important, but the metal materials are exposed to air and are easy to generate chemical and electrochemical corrosion. Corrosion of materials, especially metal corrosion, is a serious problem to be solved in the world. The corrosion not only consumes the wealth of the human beings, but also seriously hinders the normal operation of production and life, and even threatens the safety and health of the human beings. The data show that the direct economic loss caused by metal corrosion reaches to 7000 hundred million dollars each year in the world, which is 6 times of the total loss caused by other natural disasters, and the economic loss caused by corrosion in China reaches 4 percent of the total value of national production.
Various means of preventing corrosion have been developed to prevent corrosion of metals, with metal coatings being the most widely used. The anticorrosion coating technology is to cover a layer of coating with good corrosion resistance on the surface of a metal material to isolate a metal matrix from a corrosive environment, so that the corrosion speed of the metal is slowed down. The micro-arc oxidation coating has the characteristics of stable quality, excellent corrosion resistance and wear resistance, strong binding force and the like, has wide application range, and is a very good choice for metal corrosion protection technology. For the micro-arc oxidation coating, the large number of cavities in the coating becomes the biggest obstacle for limiting the further improvement of the corrosion resistance of the micro-arc oxidation coating. Therefore, in order to further improve the corrosion resistance of the micro-arc oxidation coating, the pores of the micro-arc oxidation coating must be blocked by post-treatment.
The phosphorization liquid has the characteristics of no toxicity, no harm, low cost, simple operation and the like, so that the phosphorization liquid is always paid more attention in the field of metal chemical conversion films. Particularly, the phosphating film has good combination with paint, improves corrosion resistance to a certain extent and the like, so that the phosphating film is widely used in various fields such as metal paint priming coats, rust-proof phosphating layers, wear-resistant and antifriction phosphating layers and the like.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method of an alloy self-repairing corrosion-resistant micro-arc oxidation coating, which can improve the performance of the micro-arc oxidation coating through the post-treatment of a phosphating solution containing a corrosion inhibitor and solve the defects of high micro-arc oxidation void ratio and poor corrosion resistance caused by easy invasion of a corrosion medium into a matrix at present.
The above object of the present invention is achieved by the following technical solutions:
a preparation method of an alloy self-repairing corrosion-resistant micro-arc oxidation coating comprises the following steps:
step 1, preparing a micro-arc oxidation electrolyte: fully mixing and dissolving 10-80 g/L of sodium silicate, 1-10 g/L of potassium fluoride, 0.5-8 g/L of sodium hydroxide and 10-80 mL/L of ethylene glycol in deionized water, and uniformly stirring;
step 2, pretreatment: polishing and cleaning a metal matrix by using sand paper, then ultrasonically removing oil by using acetone, cleaning by using alcohol, washing by using deionized water and drying;
step 3, preparing the micro-arc oxidation coating: and (3) carrying out in-situ preparation on the micro-arc oxidation coating on the metal matrix pretreated in the step (2) in the electrolyte prepared in the step (1), wherein a constant voltage or constant current mode is selected in the micro-arc oxidation process, and the process parameters of the micro-arc oxidation are as follows: the output voltage is 200-600V under the constant voltage mode, and the current density is 1-10A/dm under the constant current mode2The pulse duty ratio is 10% -70%, the pulse frequency is 50-5000 Hz, and the processing time is 10-60 min;
and 4, preparing a post-treatment solution: firstly, 20-60 g/L of dihydric phosphate, 1-8 g/L of sodium nitrate and 10-50 g/L of corrosion inhibitor are fully mixed and dissolved in deionized water, and the mixture is stirred uniformly; then 20-60 g/L, EDTA g/L of tetrasodium sulfate is fully mixed and dissolved, and the mixture is uniformly stirred; finally, mixing the two solutions and uniformly stirring;
and 5, immersing the metal substrate with the micro-arc oxidation coating prepared in the step 3 into the post-treatment solution prepared in the step 4 for treatment for 10-120 min at the temperature of 40-80 ℃, taking out the metal substrate, immersing the metal substrate in distilled water for washing, and aging the metal substrate for 24-72 h at normal temperature.
In the preparation method of the alloy self-repairing corrosion-resistant micro-arc oxidation coating, in the step 1, the preferable mass ratio of sodium silicate, potassium fluoride, sodium hydroxide, glycol and deionized water is 30-40: 3-4: 2-3: 30-40: 1000.
In the preparation method of the alloy self-repairing corrosion-resistant micro-arc oxidation coating, in the step 1, sodium silicate is replaced by sodium phosphate or sodium tripolyphosphate.
In the step 2, the sand paper grinding is carried out according to 240-mesh, 400-mesh, 800-mesh and 1000-mesh sand paper in sequence.
In the step 2, the metal matrix is one of magnesium alloy, aluminum alloy or titanium alloy.
In the preparation method of the alloy self-repairing corrosion-resistant micro-arc oxidation coating, in the step 3, the distance between a cathode and an anode is adjusted to be 10-1000 mm according to the size of a metal substrate on which the micro-arc oxidation coating needs to grow; preferably, the micro-arc oxidation process selects a constant voltage mode or a constant current mode, the output voltage is 300-480V in the constant voltage mode, and the current density in the constant current mode is 1-2A/dm2The pulse frequency is 100-500 Hz, and the pulse duty ratio is 25-35%.
In the step 4, the dihydric phosphate is one of ammonium dihydrogen phosphate, sodium dihydrogen phosphate or potassium dihydrogen phosphate, the sulfate is manganese sulfate or zinc sulfate, and the corrosion inhibitor is one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium fumarate, octahydroxyquinoline or sodium 3, 5 dinitrosalicylate.
According to the preparation method of the alloy self-repairing corrosion-resistant micro-arc oxidation coating, in the step 4, the pH value of the post-treatment solution is 3-6.
The design idea of the invention is as follows:
the method comprises the steps of firstly forming a layer of micro-arc oxidation coating on the metal surface in silicate electrolyte by using pulse current, and then carrying out hole sealing post-treatment in phosphating solution containing corrosion inhibitor. When the micro-arc oxidation layer is immersed in the phosphating solution, the local pH value in the micro-arc oxidation holes is increased, dihydric phosphate and sulfate in the phosphating solution react to generate water-insoluble monohydrogen phosphate crystals, crystals block the micro-arc oxidation coating holes, and a corrosion inhibitor is sealed in the micro-arc oxidation holes to reduce the porosity of the micro-arc oxidation coating and prevent a corrosive medium from entering the film through the holes to contact with a metal matrix in the use process of metal, so that the aim of improving the corrosion resistance of the film is fulfilled.
The invention has the advantages and beneficial effects that:
1) the phosphating solution disclosed by the invention is simple to operate, low in cost, durable and reliable in the post-treatment of the micro-arc oxidation coating;
2) the phosphate is crystallized above the micro-arc oxidation layer, so that the thickness of the coating is effectively increased;
3) the corrosion inhibitor can be loaded on the micro-arc oxidation coating, so that the corrosion rate of the alloy is effectively reduced;
4) according to the invention, the performance of the micro-arc oxidation coating can be improved by post-treatment of the phosphating solution containing the corrosion inhibitor, the surface porosity of the micro-arc oxidation coating is relatively low, a corrosion medium can be effectively prevented from entering, and the corrosion resistance of a matrix can be effectively improved.
Drawings
FIG. 1 is a photograph of the surface macrostructures before post-treatment by the phosphating solution.
FIG. 2 is a photograph of the surface macrostructures after post-treatment with phosphating solution.
FIG. 3 is a macroscopic corrosion morphology after a 25 day neutral salt spray test.
Detailed Description
In the specific implementation process, the hole sealing technology for the micro-arc oxidation coating based on the phosphating solution containing the corrosion inhibitor can be realized by the following key steps:
(1) preparing micro-arc oxidation growth electrolyte according to the type of the magnesium alloy for growing the oxide layer and the component type of the required oxide layer;
(2) adjusting the distance between the cathode and the anode to be 10-1000 mm according to the size of a metal matrix workpiece needing to grow an oxide layer;
(3) the micro-arc oxidation process selects a constant voltage or constant current mode, and the current density of the constant current mode is 1-10A/dm2The output voltage is 200-600V under the constant voltage mode, the regulation pulse frequency is 50-5000 Hz, and the pulse duty ratio is10-70%, and the thickness of the micro-arc oxidation coating is 10-50 μm;
(4) preparing a phosphating solution according to the component types of the required self-repairing layer, wherein the pH value is 3-6, soaking the metal with the micro-arc oxidation film in the solution to prepare a film layer through deposition reaction, the preparation temperature is 40-80 ℃, the preparation time is 10-60 min, and the porosity of the micro-arc oxidation film is 10-40%.
According to the process provided by the invention, no matter the metal anode is magnesium alloy, titanium alloy or aluminum alloy, the film layer can be successfully prepared on the surface of the metal anode. The main parameters of micro-arc oxidation need to be regulated and controlled are as follows: the concentration of each component in the electrolyte and the electrical parameters in the micro-arc oxidation process. The main parameters to be regulated and controlled in the post-treatment are as follows: the temperature and the preparation time in the preparation process of the concentration of each component in the solution.
In order that the objects, method aspects and advantages of the present invention will become more apparent, preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings. The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and together with the description, serve to explain the principles of the invention.
Example 1
In the embodiment, the surface of the AZ91D magnesium alloy is prepared by adopting electrolyte through micro-arc oxidation and deposition in phosphating solution containing corrosion inhibitor, and the method is implemented according to the following steps:
the method comprises the following steps: the preparation method of the micro-arc oxidation growth electrolyte comprises the following steps: 20g/L of sodium silicate, 4g/L of potassium fluoride, 3g/L of alkali metal sodium hydroxide, 20mL/L of ethylene glycol and the balance of deionized water;
step two: taking a metal matrix needing to grow an oxide film as an anode and a graphite plate as a cathode, and adjusting the distance between the anode and the cathode to be 200 mm; polishing and cleaning a metal substrate by using sand paper, wherein the sand paper is sequentially polished according to 240 meshes, 400 meshes, 800 meshes and 1000 meshes; then ultrasonically removing oil by using acetone, cleaning by using alcohol, washing by using deionized water and drying;
step three: selecting constant current mode with current density of 2A/dm2Regulating and controlling the pulse frequency to be 300Hz, the pulse duty ratio to be 30 percent, the processing time to be 30min and the thickness of the micro-arc oxidation coatingIs 30 μm;
step four: the components of the prepared phosphating solution are as follows: 30g/L ammonium dihydrogen phosphate, 1g/L sodium nitrate, 20g/L sodium dodecyl sulfate, 30g/L manganese sulfate monohydrate, 2g/L EDTA tetrasodium, and the balance of deionized water. The preparation process comprises the following steps: fully mixing ammonium dihydrogen phosphate, sodium nitrate and lauryl sodium sulfate, dissolving in deionized water, and uniformly stirring; fully mixing and dissolving the manganese sulfate monohydrate and the EDTA tetrasodium, and uniformly stirring; finally, mixing the two solutions and uniformly stirring;
step five: and soaking the metal with the micro-arc oxidation film in the solution to prepare the film layer through deposition reaction, wherein the preparation temperature is 70 ℃, the preparation time is 30min, then taking out the film layer to be soaked in distilled water, and aging the film layer for 48h at normal temperature, wherein the porosity of the micro-arc oxidation film is 10%.
Example 2
In the embodiment, the AM50 magnesium alloy surface is prepared by adopting electrolyte through micro-arc oxidation and deposition in phosphating solution containing corrosion inhibitor, and the method is implemented according to the following steps:
the method comprises the following steps: the preparation method of the micro-arc oxidation growth electrolyte comprises the following steps: 20g/L of sodium silicate, 4g/L of potassium fluoride, 3g/L of alkali metal sodium hydroxide, 50mL/L of ethylene glycol and the balance of deionized water;
step two: taking a metal matrix needing to grow an oxide film as an anode and a graphite plate as a cathode, and adjusting the distance between the anode and the cathode to be 200 mm; polishing and cleaning a metal substrate by using sand paper, wherein the sand paper is sequentially polished according to 240 meshes, 400 meshes, 800 meshes and 1000 meshes; then ultrasonically removing oil by using acetone, cleaning by using alcohol, washing by using deionized water and drying;
step three: selecting a constant voltage mode, controlling the voltage to be 450V, regulating and controlling the pulse frequency to be 300Hz, controlling the pulse duty ratio to be 30%, controlling the processing time to be 40min, and controlling the thickness of the micro-arc oxidation coating to be 40 mu m;
step four: the components of the prepared phosphating solution are as follows: 40g/L ammonium dihydrogen phosphate, 2g/L sodium nitrate, 15g/L sodium dodecyl sulfate, 40g/L manganese sulfate monohydrate, 2g/L EDTA tetrasodium, and the balance of deionized water. The preparation process comprises the following steps: fully mixing ammonium dihydrogen phosphate, sodium nitrate and sodium dodecyl sulfate, dissolving in deionized water, and uniformly stirring; fully mixing and dissolving the manganese sulfate monohydrate and the EDTA tetrasodium, and uniformly stirring; finally, mixing the two solutions and uniformly stirring;
step five: and soaking the metal with the micro-arc oxidation film in the solution to prepare the film layer through deposition reaction, wherein the preparation temperature is 80 ℃, the preparation time is 60min, then taking out the film layer to be soaked in distilled water, and aging the film layer for 24h at normal temperature, wherein the porosity of the micro-arc oxidation film is 12%.
Example 3
In the embodiment, the surface of the ZK60 magnesium alloy is prepared by adopting electrolyte through micro-arc oxidation and deposition in phosphating solution containing corrosion inhibitor, and the method is implemented according to the following steps:
the method comprises the following steps: the preparation method of the micro-arc oxidation growth electrolyte comprises the following steps: 30g/L of sodium silicate, 4g/L of potassium fluoride, 2g/L of alkali metal sodium hydroxide, 30mL/L of ethylene glycol and the balance of deionized water;
step two: taking a metal matrix needing to grow an oxide film as an anode and a graphite plate as a cathode, and adjusting the distance between the anode and the cathode to be 200 mm; polishing and cleaning a metal substrate by using sand paper, wherein the sand paper is sequentially polished according to 240 meshes, 400 meshes, 800 meshes and 1000 meshes; then ultrasonically removing oil by using acetone, cleaning by using alcohol, washing by using deionized water and drying;
step three: selecting constant current mode with current density of 1A/dm2Regulating and controlling the pulse frequency to be 500Hz, the pulse duty ratio to be 30%, the treatment time to be 60min, and the thickness of the micro-arc oxidation coating to be 35 mu m;
step four: the components of the prepared phosphating solution are as follows: 30g/L ammonium dihydrogen phosphate, 1g/L sodium nitrate, 30g/L sodium dodecyl benzene sulfonate, 30g/L manganese sulfate monohydrate, 2g/L EDTA tetrasodium, and the balance of deionized water. The preparation process comprises the following steps: fully mixing ammonium dihydrogen phosphate, sodium nitrate and sodium dodecyl benzene sulfonate, dissolving in deionized water, and uniformly stirring; fully mixing and dissolving the manganese sulfate monohydrate and the EDTA tetrasodium, and uniformly stirring; finally, mixing the two solutions and uniformly stirring;
step five: and soaking the metal with the micro-arc oxidation film in the solution to prepare the film layer through deposition reaction, wherein the preparation temperature is 70 ℃, the preparation time is 30min, then taking out the film layer to be soaked in distilled water, and aging the film layer for 36h at normal temperature, wherein the porosity of the micro-arc oxidation film is 20%.
Example 4
In the embodiment, the surface of the AZ91D magnesium alloy is prepared by adopting electrolyte through micro-arc oxidation and deposition in phosphating solution containing corrosion inhibitor, and the method is implemented according to the following steps:
the method comprises the following steps: the preparation method of the micro-arc oxidation growth electrolyte comprises the following steps: 60g/L of sodium silicate, 4g/L of potassium fluoride, 2g/L of alkali metal sodium hydroxide, 40mL/L of ethylene glycol and the balance of deionized water;
step two: taking a metal matrix needing to grow an oxide film as an anode and a graphite plate as a cathode, and adjusting the distance between the anode and the cathode to be 200 mm; polishing and cleaning a metal substrate by using sand paper, wherein the sand paper is sequentially polished according to 240 meshes, 400 meshes, 800 meshes and 1000 meshes; then ultrasonically removing oil by using acetone, cleaning by using alcohol, washing by using deionized water and drying;
step three: selecting constant current mode with current density of 2A/dm2Regulating and controlling the pulse frequency to be 500Hz, the pulse duty ratio to be 30 percent, the processing time to be 50min and the thickness of the micro-arc oxidation coating to be 50 mu m;
step four: the components of the prepared phosphating solution are as follows: 30g/L ammonium dihydrogen phosphate, 1g/L sodium nitrate, 40g/L sodium fumarate, 30g/L manganese sulfate monohydrate, 2g/L EDTA tetrasodium, and the balance of deionized water. The preparation process comprises the following steps: firstly, fully mixing ammonium dihydrogen phosphate, sodium nitrate and sodium fumarate, dissolving in deionized water, and uniformly stirring; fully mixing and dissolving the manganese sulfate monohydrate and the EDTA tetrasodium, and uniformly stirring; finally, mixing the two solutions and uniformly stirring;
step five: and soaking the metal with the micro-arc oxidation film in the solution to prepare the film layer through deposition reaction, wherein the preparation temperature is 60 ℃, the preparation time is 30min, then taking out the film layer to be soaked in distilled water, and aging the film layer for 72h at normal temperature, wherein the porosity of the micro-arc oxidation film is 15%.
As shown in the figures 1-2, the comparison of the surface macro-topography photographs before and after the phosphating solution post-treatment shows that the surface roughness of the sample after the phosphating solution post-treatment is increased, a layer of phosphating film uniformly grows, and phosphate crystals are crystallized on the surface of the micro-arc oxidation coating.
As shown in fig. 3, the magnesium alloy substrate comprises an oxide layer grown on the surface of the magnesium alloy substrate and a phosphate layer deposited on the surface of the oxide layer. The oxide layer is prepared on the surface of the metal through micro-arc oxidation by adopting electrolyte, and the phosphate layer is prepared by depositing phosphating solution on the surface of the oxide layer. The macroscopic corrosion morphology after 25 days of neutral salt spray test shows that no obvious corrosion is found on the surface, which indicates that the composite coating after the phosphating solution post-treatment has excellent corrosion resistance.
Example 5
In the embodiment, the 3003 aluminum alloy surface is prepared by adopting electrolyte through micro-arc oxidation and deposition in phosphating solution containing corrosion inhibitor, and the method is implemented according to the following steps:
the method comprises the following steps: the preparation method of the micro-arc oxidation growth electrolyte comprises the following steps: 40g/L of sodium phosphate, 3g/L of potassium fluoride, 3g/L of alkali metal sodium hydroxide, 35mL/L of ethylene glycol and the balance of deionized water;
step two: taking a metal matrix needing to grow an oxide film as an anode and a graphite plate as a cathode, and adjusting the distance between the anode and the cathode to be 100 mm; polishing and cleaning a metal substrate by using sand paper, wherein the sand paper is sequentially polished according to 240 meshes, 400 meshes, 800 meshes and 1000 meshes; then ultrasonically removing oil by using acetone, cleaning by using alcohol, washing by using deionized water and drying;
step three: selecting a constant voltage mode, controlling the voltage to be 350V, regulating and controlling the pulse frequency to be 400Hz, controlling the pulse duty ratio to be 35%, controlling the processing time to be 40min, and controlling the thickness of the micro-arc oxidation coating to be 15 mu m;
step four: the components of the prepared phosphating solution are as follows: 45g/L of sodium dihydrogen phosphate, 3g/L of sodium nitrate, 25g/L of octohydroxyquinoline, 35g/L of zinc sulfate, 5g/L of tetrasodium EDTA and the balance of deionized water. The preparation process comprises the following steps: firstly, fully mixing and dissolving sodium dihydrogen phosphate, sodium nitrate and octohydroxyquinoline in deionized water, and uniformly stirring; then, fully mixing and dissolving zinc sulfate and EDTA tetrasodium, and uniformly stirring; finally, mixing the two solutions and uniformly stirring;
step five: and soaking the metal with the micro-arc oxidation film in the solution to prepare the film layer through deposition reaction, wherein the preparation temperature is 50 ℃, the preparation time is 60min, then taking out the film layer to be soaked in distilled water, and aging the film layer for 24h at normal temperature, wherein the porosity of the micro-arc oxidation film is 15%.
Example 6
In the embodiment, the surface of the TC4 titanium alloy is prepared by adopting electrolyte through micro-arc oxidation and deposition in phosphating solution containing corrosion inhibitor, and the method is implemented according to the following steps:
the method comprises the following steps: the preparation method of the micro-arc oxidation growth electrolyte comprises the following steps: 35g/L of sodium tripolyphosphate, 4g/L of potassium fluoride, 2g/L of alkali metal sodium hydroxide, 30mL/L of ethylene glycol and the balance of deionized water;
step two: taking a metal matrix needing to grow an oxide film as an anode and a graphite plate as a cathode, and adjusting the distance between the anode and the cathode to be 50 mm; polishing and cleaning a metal substrate by using sand paper, wherein the sand paper is sequentially polished according to 240 meshes, 400 meshes, 800 meshes and 1000 meshes; then ultrasonically removing oil by using acetone, cleaning by using alcohol, washing by using deionized water and drying;
step three: selecting constant current mode with current density of 1.5A/dm2Regulating and controlling the pulse frequency to be 350Hz, the pulse duty ratio to be 25 percent, the processing time to be 30min and the thickness of the micro-arc oxidation coating to be 10 mu m;
step four: the components of the prepared phosphating solution are as follows: 50g/L potassium dihydrogen phosphate, 4g/L sodium nitrate, 35 g/L3, 5-dinitro sodium salicylate, 40g/L zinc sulfate, 3g/L EDTA tetrasodium and the balance of deionized water. The preparation process comprises the following steps: firstly, fully mixing and dissolving potassium dihydrogen phosphate, sodium nitrate and 3, 5-dinitro sodium salicylate in deionized water, and uniformly stirring; then, fully mixing and dissolving zinc sulfate and EDTA tetrasodium, and uniformly stirring; finally, mixing the two solutions and uniformly stirring;
step five: and soaking the metal with the micro-arc oxidation film in the solution to prepare the film layer through deposition reaction, wherein the preparation temperature is 80 ℃, the preparation time is 40min, then taking out the film layer to be soaked in distilled water, and aging the film layer for 48h at normal temperature, wherein the porosity of the micro-arc oxidation film is 10%.
The embodiment result shows that compared with the prior art, the micro-arc oxidation hole sealing coating provided by the invention has a better protection effect in a corrosive environment, and has the following advantages as a workpiece: (a) a denser film layer and lower porosity; (b) the corrosion inhibitor has a strong barrier effect on the invasion of corrosive media; (c) the thickness and the structure of the film layer are uniform; (d) the film layer has strong binding force with the substrate and strong capability of resisting external force damage; (e) the preparation of the film layer is simple, the requirement on equipment is low, and the large-scale production and the preparation of complex workpieces are easy.
Claims (6)
1. A preparation method of a magnesium alloy self-repairing corrosion-resistant micro-arc oxidation coating is characterized in that a pulse current is utilized on the surface of a metal to form a layer of micro-arc oxidation coating in a silicate electrolyte, and hole sealing post-treatment is carried out in a phosphating solution containing a corrosion inhibitor, and comprises the following steps:
step 1, preparing a micro-arc oxidation electrolyte: fully mixing and dissolving 10-80 g/L of sodium silicate, 1-10 g/L of potassium fluoride, 0.5-8 g/L of sodium hydroxide and 10-80 mL/L of ethylene glycol in deionized water, and uniformly stirring;
step 2, pretreatment: polishing and cleaning a magnesium alloy substrate by using abrasive paper, then ultrasonically removing oil by using acetone, cleaning by using alcohol, washing by using deionized water and drying;
step 3, preparing the micro-arc oxidation coating: and (3) carrying out in-situ preparation on the micro-arc oxidation coating on the magnesium alloy substrate pretreated in the step (2) in the electrolyte prepared in the step (1), wherein a constant voltage or constant current mode is selected in the micro-arc oxidation process, and the process parameters of the micro-arc oxidation are as follows: the output voltage is 200-600V under the constant voltage mode, and the current density is 1-10A/dm under the constant current mode2The pulse duty ratio is 10% -70%, the pulse frequency is 50-500 Hz, the treatment time is 30-60 min, and the thickness of the micro-arc oxidation coating is 10-50 mu m;
and 4, preparing a post-treatment solution: firstly, 20-60 g/L of dihydric phosphate, 1-8 g/L of sodium nitrate and 10-50 g/L of corrosion inhibitor are fully mixed and dissolved in deionized water, and the mixture is stirred uniformly; then 20-60 g/L, EDTA g/L of tetrasodium sulfate is fully mixed and dissolved, and the mixture is uniformly stirred; finally, mixing the two solutions and uniformly stirring; when the micro-arc oxidation layer is immersed in the phosphating solution, the local pH value in the micro-arc oxidation holes is increased, dihydric phosphate in the phosphating solution reacts with sulfate to generate water-insoluble monohydrogen phosphate crystals, the crystals block the micro-arc oxidation coating holes, and a corrosion inhibitor is sealed in the micro-arc oxidation holes;
wherein, the dihydric phosphate is one of ammonium dihydrogen phosphate, sodium dihydrogen phosphate or potassium dihydrogen phosphate, the sulfate is manganese sulfate or zinc sulfate, and the corrosion inhibitor is one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium fumarate, octahydroxyquinoline or 3, 5 dinitro sodium salicylate;
and 5, immersing the magnesium alloy substrate with the micro-arc oxidation coating prepared in the step 3 into the post-treatment solution prepared in the step 4 for treatment for 10-120 min at the temperature of 40-80 ℃, taking out, immersing in distilled water for washing, and aging for 24-72 h at normal temperature.
2. The preparation method of the magnesium alloy self-repairing corrosion-resistant micro-arc oxidation coating according to claim 1, wherein in the step 1, the mass ratio of the sodium silicate to the potassium fluoride to the sodium hydroxide to the ethylene glycol to the deionized water is 30-40: 3-4: 2-3: 30-40: 1000.
3. The preparation method of the magnesium alloy self-repairing corrosion-resistant micro-arc oxidation coating is characterized by comprising the following steps of:
step 1, preparing a micro-arc oxidation electrolyte: fully mixing and dissolving 10-80 g/L sodium phosphate or sodium tripolyphosphate, 1-10 g/L potassium fluoride, 0.5-8 g/L sodium hydroxide and 10-80 mL/L ethylene glycol in deionized water, and uniformly stirring;
step 2, pretreatment: polishing and cleaning a magnesium alloy substrate by using abrasive paper, then ultrasonically removing oil by using acetone, cleaning by using alcohol, washing by using deionized water and drying;
step 3, preparing the micro-arc oxidation coating: and (3) carrying out in-situ preparation on the micro-arc oxidation coating on the magnesium alloy substrate pretreated in the step (2) in the electrolyte prepared in the step (1), wherein a constant voltage or constant current mode is selected in the micro-arc oxidation process, and the process parameters of the micro-arc oxidation are as follows: the output voltage is 200-600V under the constant voltage mode, and the current density is 1-10A/dm under the constant current mode2The pulse duty ratio is 10% -70%, the pulse frequency is 50-500 Hz, and the processing time is 30-60 minThe thickness of the micro-arc oxidation coating is 10-50 mu m;
and 4, preparing a post-treatment solution: firstly, 20-60 g/L of dihydric phosphate, 1-8 g/L of sodium nitrate and 10-50 g/L of corrosion inhibitor are fully mixed and dissolved in deionized water, and the mixture is stirred uniformly; then 20-60 g/L, EDTA g/L of tetrasodium sulfate is fully mixed and dissolved, and the mixture is uniformly stirred; finally, mixing the two solutions and uniformly stirring; when the micro-arc oxidation layer is immersed in the phosphating solution, the local pH value in the micro-arc oxidation holes is increased, dihydric phosphate in the phosphating solution reacts with sulfate to generate water-insoluble monohydrogen phosphate crystals, the crystals block the micro-arc oxidation coating holes, and a corrosion inhibitor is sealed in the micro-arc oxidation holes;
wherein, the dihydric phosphate is one of ammonium dihydrogen phosphate, sodium dihydrogen phosphate or potassium dihydrogen phosphate, the sulfate is manganese sulfate or zinc sulfate, and the corrosion inhibitor is one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium fumarate, octahydroxyquinoline or 3, 5 dinitro sodium salicylate;
and 5, immersing the magnesium alloy substrate with the micro-arc oxidation coating prepared in the step 3 into the post-treatment solution prepared in the step 4 for treatment for 10-120 min at the temperature of 40-80 ℃, taking out, immersing in distilled water for washing, and aging for 24-72 h at normal temperature.
4. The preparation method of the magnesium alloy self-repairing corrosion-resistant micro-arc oxidation coating according to claim 1 or 3, wherein in the step 2, the sand paper grinding is carried out according to 240-mesh, 400-mesh, 800-mesh and 1000-mesh sand paper in sequence.
5. The preparation method of the magnesium alloy self-repairing corrosion-resistant micro-arc oxidation coating according to claim 1 or 3, characterized in that in the step 3, the distance between the cathode and the anode is adjusted to 10-1000 mm according to the size of the magnesium alloy substrate on which the micro-arc oxidation coating needs to grow; the micro-arc oxidation process selects a constant voltage or constant current mode, the output voltage is 300-480V under the constant voltage mode, and the current density of the constant current mode is 1-2A/dm2The pulse frequency is 100-500 Hz, and the pulse duty ratio is 25-35%.
6. The preparation method of the magnesium alloy self-repairing corrosion-resistant micro-arc oxidation coating according to claim 1 or 3, wherein in the step 4, the pH value of the post-treatment solution is 3-6.
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