CN115403945B - Composite anti-corrosion coating on magnesium alloy surface and preparation method thereof - Google Patents
Composite anti-corrosion coating on magnesium alloy surface and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a magnesium alloy surface composite anti-corrosion coating and a preparation method thereof, belonging to the technical field of material surface modification and protection. The coating comprises the following raw materials in percentage by mass as 100 percent: 83% -90% of Al powder, al 2 O 3 9.5 to 15 percent of powder and 0.5 to 2.0 percent of graphene oxide powder; the coating is prepared by coupling graphene oxide with part of Al powder to obtain graphene oxide coated Al composite powder, and then coupling the rest of Al powder and Al 2 O 3 Uniformly mixing the powder and the graphene oxide coated Al composite powder, and then carrying out cold spraying on the surface of the magnesium alloy, wherein the powder and the graphene oxide coated Al composite powder are prepared from Al and Al 2 O 3 And graphene oxide. The coating can achieve excellent corrosion resistance to magnesium alloy.
Description
Technical Field
The invention relates to a magnesium alloy surface composite anti-corrosion coating and a preparation method thereof, belonging to the technical field of material surface modification and protection.
Background
The magnesium alloy material has lower density, higher specific strength and specific rigidity, and has wide application prospect and value in the fields of automobiles, aerospace and weaponry. However, the magnesium alloy material has extremely low corrosion potential, and strong uniform corrosion and self-corrosion phenomena can occur in a humid environment, so that the application of the magnesium alloy material is extremely limited, and therefore, the development of the corrosion-resistant protective coating has important significance for magnesium alloy engineering application.
The novel surface modification and protection technology can realize coating deposition in a low temperature state, the compressed gas accelerates spraying powder to strike a substrate, the powder and the substrate are subjected to severe plastic deformation to form a coating in a combined mode, the temperature in the spraying process is lower than the melting point of sprayed particles, the particles are not subjected to a melting-resolidification process, and phenomena of oxidation, burning loss, phase change and the like of materials in the spraying process are effectively avoided. Meanwhile, the temperature in the spraying process is lower, the powder material basically does not react in the spraying process, and the microstructure and the components of the coating are consistent with the characteristics of the original powder material, so that the excellent coating can be obtained by controlling the components, the particle size and the morphology of the powder. The coating has high deposition efficiency and low porosity, and a great deal of research has been carried out in the aspect of preparing wear-resistant and corrosion-resistant coatingsWork is performed. For example, the surface of the magnesium alloy is prepared with 316L/WC, 420 stainless steel and Al by adopting cold spraying 2 O 3 And (5) an abrasion-resistant coating. The pure aluminum coating is cold-sprayed on the surface of the magnesium alloy, so that the coating with excellent corrosion resistance can be obtained, but the pure aluminum coating prepared by cold spraying is not compact and has poor combination with a matrix, and the pure aluminum coating also has the problems of low hardness, poor wear resistance and the like, so that the application of the cold-sprayed pure aluminum coating is severely restricted. The ceramic strengthening phase is added into the pure aluminum powder during cold spraying, so that the problems can be effectively solved, and the wear-resistant and corrosion-resistant integrated protective coating can be prepared.
The graphene has excellent properties of good barrier property, high mechanical strength, large specific surface area and the like, has a great application prospect in protecting a matrix by adding the graphene into a metal-based anti-corrosion coating, and is widely applied to the fields of anti-corrosion coatings and coatings. However, as the graphene sheets have strong intermolecular force, the graphene sheets are unevenly dispersed in the spraying composite powder, so that holes are formed in the coating, and corrosion medium is easier to infiltrate into the metal matrix. Therefore, improving the dispersion effect and stability of graphene in composite powder and coating becomes the research difficulty and focus of graphene-based anticorrosive paint/coating. Graphene oxide is used as an important derivative of a graphene-based material, the special surface property and the lamellar structure are maintained, and the introduction of oxygen-containing groups not only enables the graphene oxide to have chemical stability, but also provides a surface modification active position and a larger specific surface area for synthesizing the graphene-based/graphene-based material. Graphene oxide is similar to graphene in terms of performance function, and is also used in anticorrosive coatings. The current common method is to mix metal powder with graphene oxide and ball-mill the mixture, but a longer ball-milling time is generally required to break particles and change the shape and size of the particles, and the application of graphene oxide in the anti-corrosion field has an important influence on the integrity of graphene sheets when preparing a graphene oxide coating. In addition, graphene oxide and aluminum are subjected to in-situ reduction reaction to prepare a graphene coated aluminum composite material, so that graphene is uniformly coated on the surface of aluminum powder, but the method relies on electrostatic adsorption between graphene and aluminum powder, so that the binding force is limited, the reaction control difficulty is high, and the coating effect is relatively poor.
Disclosure of Invention
In view of the above, the invention aims to provide a magnesium alloy surface composite anti-corrosion coating and a preparation method thereof.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the composite anticorrosive coating for the magnesium alloy surface comprises the following components in percentage by mass as per 100% of raw materials for preparing the coating: 83% -90% of Al powder, al 2 O 3 9.5 to 15 percent of powder and 0.5 to 2.0 percent of graphene oxide powder; the coating is prepared by coupling graphene oxide with part of Al powder to obtain graphene oxide coated Al composite powder, and then coupling the rest of Al powder and Al 2 O 3 Uniformly mixing the powder and the graphene oxide coated Al composite powder, and then carrying out cold spraying on the surface of the magnesium alloy, wherein the powder and the graphene oxide coated Al composite powder are prepared from Al and Al 2 O 3 And graphene oxide.
Preferably, the mass fraction of the Al powder is 83-85%, al 2 O 3 The mass fraction of the powder is 13.5-15%, and the mass fraction of the graphene oxide powder is 1.5-2.0%.
The invention relates to a preparation method of a composite anti-corrosion coating on the surface of a magnesium alloy, which comprises the following steps:
(1) Uniformly mixing graphene oxide with water with the conductivity less than or equal to 1us/cm to obtain a graphene oxide aqueous solution; dissolving a coupling agent in an organic solvent to obtain a coupling agent solution; adding a silane coupling agent solution into a graphene oxide aqueous solution, uniformly dispersing by ultrasonic, adjusting the pH to 4-5 by using an acid solution, heating to 50-80 ℃, and reacting for 2-4 hours to obtain a reaction solution;
(2) Adding part of Al powder into the reaction liquid, heating to 50+/-5 ℃, sealing and preserving heat for 30-60 min, after the reaction is finished, carrying out solid-liquid separation, collecting solid, washing and drying to obtain graphene oxide coated Al composite powder;
(3) Residual Al powder and Al 2 O 3 Uniformly mixing the powder and the graphene oxide coated Al composite powderAnd then, loading the magnesium alloy into a powder feeder of cold spraying equipment for cold spraying, and obtaining a composite anti-corrosion coating on the surface of the magnesium alloy matrix after heat treatment.
Preferably, the Al powder has a particle size of 5-50 μm, al 2 O 3 The particle size of the powder is 20-30 mu m, and the particle size of the graphene oxide powder is 0.1-2 mu m.
Preferably, in step (1), the organic solvent is absolute ethanol or isopropanol.
Preferably, in the step (1), the coupling agent is a silane coupling agent (such as KH550, KH560, KH570 or KH 845-4), a titanate coupling agent or an aluminate coupling agent; the addition amount of the coupling agent is 0.5-1.5% of the total mass of the graphene oxide and the Al powder in the step (2).
Preferably, in the step (2), the amount of the Al powder is 20% -50% of the total mass of the Al powder.
Preferably, in the step (3), the surface of the substrate is subjected to sand blasting treatment before cold spraying to remove surface oxides, and the surface roughness Ra is 1.6-3.2 μm after sand blasting treatment.
Preferably, in the step (3), during cold spraying, the carrier gas is compressed air or nitrogen, and the cold spraying process parameters are as follows: the pressure is 0.5 MPa-1.5 MPa, the temperature is 300-500 ℃, the powder feeding speed is 0.5L/min-1.5L/min, the moving speed of the spray gun is 0.02 m/s-0.04 m/s, and the spraying distance is 10 mm-20 mm.
Preferably, in the step (3), the degree of vacuum is 10 during the heat treatment -1 Pa～10 -2 Pa, the temperature is 300-400 ℃, the temperature is kept for 4-6 h, and an Al/Al is obtained on the surface of the magnesium alloy matrix after cooling 2 O 3 And (3) a graphene oxide composite anticorrosive coating.
Advantageous effects
The invention provides a composite anti-corrosion coating for the surface of magnesium alloy, which is prepared from specific content of Al and Al 2 O 3 And graphene oxide are compounded, and a hard A1 is added into the coating 2 O 3 Ceramic particles, which tamp the coating deposition to make the coating more dense, and A1 2 O 3 The ceramic material has high hardness and stabilityGood and the like, the graphene oxide has excellent corrosion resistance, and the prepared Al/Al is prepared by combining the phase functions and characteristics of a coating 2 O 3 The graphene oxide composite coating can achieve an excellent corrosion resistance effect on the magnesium alloy.
The invention provides a preparation method of a composite anti-corrosion coating on the surface of magnesium alloy, which adopts a cold spraying technology to spray Al powder and Al 2 O 3 The powder and the graphene oxide powder can be sprayed at a lower temperature to prepare the coating, and compared with the conventional thermal spraying technology, the three components are prevented from being damaged by oxidation or crystal forms in the spraying process.
The invention provides a preparation method of a composite anticorrosive coating on the surface of a magnesium alloy, which is characterized in that graphene oxide and Al powder are subjected to coupling treatment, a layer of graphene oxide is coated on the surface of the Al powder, and the graphene oxide coated Al composite powder with stronger combination and uniform distribution is prepared, so that the problems of graphene oxide agglomeration in the coating and contribution to the deposition of the graphene oxide are solved.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
Selecting a powder material: the grain diameter of Al powder is 5-50 mu m, al 2 O 3 The powder is 20-30 mu M, the graphene oxide powder is 0.1-2 mu M, the LA43M magnesium lithium alloy is used as a matrix, and the sample size is phi 30mm multiplied by 10mm.
2g of graphene oxide is taken and dissolved in 100mL of deionized water, and the mixture is stirred and mixed uniformly. The silane coupling agent KH560 was dissolved in 200mL of an absolute ethanol solvent, and stirred to dissolve, thereby forming a coupling agent solution with a mass concentration of 0.5%. Adding the coupling agent solution into the graphene oxide aqueous solution, performing ultrasonic treatment for 15-30 min, adjusting the pH value to 4-5 by using hydrochloric acid, and then performing reaction in a water bath at 60 ℃ for 4h to obtain a reaction solution. Then 50g of Al powder is added into the reaction liquid, and the reaction liquid is heated by a constant-temperature water bath, the temperature is controlled to be 50+/-5 ℃, and the heat preservation time is 30-60 min. The vessel was sealed during incubation to prevent solvent evaporation. Centrifuging and steaming to remove the solvent after the reaction, washing the composite powder for 2-3 times by using absolute ethyl alcohol, and removing unreacted coupling agent. Finally, drying treatment is carried out in an oven, and heat preservation is carried out for 2 hours at 80 ℃ to finally obtain the coupled graphene oxide coated Al composite powder with strong binding force and good dispersibility.
Before cold spraying, the surface of the substrate is required to be subjected to sand blasting treatment to remove surface oxides, and the surface roughness Ra of the substrate is 3.2 mu m after sand blasting treatment.
Al powder, al 2 O 3 After powder and graphene oxide coated Al composite powder are mechanically and uniformly mixed according to the mass ratio of 40:10:50, the mixture is preserved in a drying oven at 80 ℃ for 2 hours, and then the mixture is placed in a powder feeder of cold spraying equipment, wherein carrier gas for cold spraying is nitrogen, and the cold spraying technological parameters are as follows: the gas pressure is 0.8MPa, the gas temperature is 300 ℃, the powder feeding speed is 0.5L/min, the moving speed of a spray gun is 0.02m/s, the spraying distance is 15mm, and the Al/Al is obtained on the surface of a substrate 2 O 3 Graphene oxide composite anticorrosive coating, and carrying out heat treatment on the coating in a vacuum tube type heat treatment furnace, wherein the vacuum degree is 10 -1 ～10 -2 Pa, the temperature is 300 ℃, the temperature is kept for 6 hours, and the furnace cooling is carried out.
The thickness of the coating was measured using a coating thickness gauge and was 86 μm. The adhesion of the coating was tested using a Positest AT adhesion tester, with an adhesion of 31.6MPa. The corrosion current density of the coating was tested using an electrochemical workstation, and the self-corrosion current density of the coating was 1.015×10 -7 A/cm 2 Compared with the magnesium alloy matrix (1.525×10) -4 A/cm 2 ) The amount is reduced by 3 orders of magnitude, and the aim of corrosion prevention is achieved.
Example 2:
the powder material is selected to be Al powder with the grain diameter of 5-50 mu m, al 2 O 3 The powder is 20-30 mu M, the graphene oxide powder is 0.1-2 mu M, the LA43M magnesium lithium alloy is used as a matrix, and the sample size is phi 30mm multiplied by 10mm.
Before cold spraying, the surface of the substrate is required to be subjected to sand blasting treatment to remove surface oxides, and the surface roughness Ra of the substrate is 3.2 mu m after sand blasting treatment.
The same coupling treatment method as in example 1 was used to prepare graphene oxide coated Al composite powder.
Al powder, al 2 O 3 After the powder and the graphene oxide/Al composite powder are mechanically and uniformly mixed according to the mass ratio of 25:15:60, the mixture is preserved in a drying oven at 80 ℃ for 2 hours, then the mixture is placed in a powder feeder of cold spraying equipment, and the mixed powder is sprayed on the surface of a magnesium-lithium alloy matrix. Wherein, the carrier gas of cold spraying is nitrogen, and the cold spraying technological parameters are: the gas pressure is 0.9MPa, the gas temperature is 400 ℃, the powder feeding speed is 0.5L/min, the moving speed of a spray gun is 0.02m/s, the spraying distance is 10mm, and the Al/Al is obtained by cold spraying on the surface of a substrate 2 O 3 Graphene oxide composite anticorrosive coating, and carrying out heat treatment on the coating in a vacuum tube type heat treatment furnace, wherein the vacuum degree is 10 -1 ～10 -2 Pa, the temperature is 400 ℃, the temperature is kept for 4 hours, and the furnace cooling is carried out.
The thickness of the coating was measured using a coating thickness gauge and was 58 μm. The adhesion of the coating was tested using a Positest AT adhesion tester, with an adhesion of 28.5MPa. The corrosion current density of the coating was tested using an electrochemical workstation, and the self-corrosion current density of the coating was 5.642 ×10 -8 A/cm 2 Compared with the magnesium alloy matrix (1.525×10) -4 A/cm 2 ) The corrosion resistance is achieved by reducing the number of orders of magnitude by 4.
Comparative example 1:
selecting powder raw materials: the grain diameter of Al powder is 20-50 mu m, al 2 O 3 The powder is 20-30 mu M, the graphene oxide powder is 0.1-2 mu M, the LA43M magnesium lithium alloy is used as a matrix, and the sample size is phi 30mm multiplied by 10mm. The mass fraction of the Al powder is 88 percent based on 100 percent of the total mass of the raw materials, and the Al powder is 2 O 3 The mass fraction of the powder is 10%, and the mass fraction of the graphene oxide powder is 2%.
Before cold spraying, the surface of the substrate is required to be subjected to sand blasting treatment to remove surface oxides, and the surface roughness Ra of the substrate is 3.2 mu m after sand blasting treatment.
Al powder, al 2 O 3 After the powder and the graphene oxide powder are mechanically mixed uniformly, the mixture is preserved for 2 hours in a drying oven at 80 ℃, then the mixture is placed in a powder feeder of cold spraying equipment, the carrier gas for cold spraying is nitrogen,the spraying process parameters are as follows: the gas pressure is 0.8MPa, the gas temperature is 300 ℃, the powder feeding speed is 0.5L/min, the moving speed of a spray gun is 0.02m/s, the spraying distance is 15mm, and the Al/Al is obtained by cold spraying on the surface of a substrate 2 O 3 Graphene oxide composite anticorrosive coating, and carrying out heat treatment on the coating in a vacuum tube type heat treatment furnace, wherein the vacuum degree is 10 -1 ～10 -2 Pa, the temperature is 300 ℃, the temperature is kept for 6 hours, and the furnace cooling is carried out.
The thickness of the coating was measured using a coating thickness gauge and was 93 μm. The adhesion of the coating was tested using a Positest AT adhesion tester, with an adhesion of 32.7MPa. The corrosion current density of the coating was tested using an electrochemical workstation, and the self-corrosion current density of the coating was 3.204 ×10 -6 A/cm 2 。
Preparation of Al/Al by Cold spray 2 O 3 In the process of the Graphene Oxide (GO) composite coating, the graphene oxide cannot be completely deposited by adopting cold spraying due to the fact that the graphene oxide is small in size, light in weight and free of plastic deformation. Even after the graphene oxide is mixed with the Al powder, the graphene oxide powder with lighter mass is easy to be subjected to the action of shock waves on the surface of the substrate to reduce the speed and blow off before reaching the substrate in the spraying process; moreover, the graphene oxide powder has small particle size and light weight, and the kinetic energy of the graphene oxide powder cannot meet the energy required by deformation of particles and a substrate, so that the difficulty of effective deposition of the graphene oxide powder by cold spraying in the embodiment is very high. Thus, cold spray is used to prepare Al/Al 2 O 3 The key point of the Graphene Oxide (GO) composite coating is that graphene oxide is uniformly and dispersedly coated on the surface of pure Al powder with better plastic deformation, so that a compact and uniform coating is hopefully prepared. According to the invention, graphene oxide powder is modified to be attached to the surface of Al powder particles with better plastic deformation, and the graphene oxide powder is carried by the Al powder particles to be co-deposited on the surface of a matrix.
In view of the foregoing, it will be appreciated that the invention includes but is not limited to the foregoing embodiments, any equivalent or partial modification made within the spirit and principles of the invention.
Claims (5)
1. The composite anticorrosive coating for the surface of the magnesium alloy is characterized in that: the coating comprises the following raw materials in percentage by mass as 100 percent: 83% -85% of Al powder, al 2 O 3 13.5-15% of powder, 1.5-2.0% of graphene oxide powder; the coating is prepared by coupling graphene oxide with part of Al powder to obtain graphene oxide coated Al composite powder, and then coupling the rest of Al powder and Al 2 O 3 Uniformly mixing the powder and the graphene oxide coated Al composite powder, and then carrying out cold spraying on the surface of the magnesium alloy, wherein the powder and the graphene oxide coated Al composite powder are prepared from Al and Al 2 O 3 And graphene oxide;
the coating is prepared by the following steps:
(1) Uniformly mixing graphene oxide with water with the conductivity less than or equal to 1us/cm to obtain a graphene oxide aqueous solution; dissolving a coupling agent in an organic solvent to obtain a coupling agent solution; adding a silane coupling agent solution into a graphene oxide aqueous solution, uniformly dispersing by ultrasonic, adjusting the pH to 4-5 by using an acid solution, heating to 50-80 ℃, and reacting for 2-4 hours to obtain a reaction solution;
(2) Adding part of Al powder into the reaction liquid, heating to 50+/-5 ℃, sealing and preserving heat for 30-60 min, after the reaction is finished, carrying out solid-liquid separation, collecting solid, washing and drying to obtain graphene oxide coated Al composite powder;
(3) Residual Al powder and Al 2 O 3 Uniformly mixing the powder and the graphene oxide coated Al composite powder, loading the mixture into a powder feeder of cold spraying equipment for cold spraying, and obtaining a composite anti-corrosion coating on the surface of a magnesium alloy matrix after heat treatment;
the addition amount of the coupling agent is 0.5% -1.5% of the total mass of graphene oxide and part of Al powder in the step (2);
the consumption of the part of Al powder is 20% -50% of the total mass of the Al powder;
in cold spraying, the carrier gas is compressed air or nitrogen, and the cold spraying process parameters are as follows: the pressure is 0.5-1.5 MPa, the temperature is 300-500 ℃, the powder feeding speed is 0.5-1.5L/min, the moving speed of the spray gun is 0.02-0.04 m/s, and the spraying distance is 10-20 mm;
vacuum degree is 10 during heat treatment -1 Pa~10 -2 Pa, the temperature is 300-400 ℃, the temperature is kept for 4-6 hours, and a composite anti-corrosion coating is obtained on the surface of the magnesium alloy matrix after cooling.
2. A composite corrosion resistant coating for a magnesium alloy surface as set forth in claim 1, wherein: the grain diameter of the Al powder is 5-50 mu m, and Al 2 O 3 The particle size of the powder is 20-30 mu m, and the particle size of the graphene oxide powder is 0.1-2 mu m.
3. A composite corrosion resistant coating for a magnesium alloy surface as set forth in claim 1, wherein: in the step (1), the organic solvent is absolute ethyl alcohol or isopropanol.
4. A composite corrosion resistant coating for a magnesium alloy surface as set forth in claim 1, wherein: in the step (1), the coupling agent is a silane coupling agent, a titanate coupling agent or an aluminate coupling agent.
5. A composite corrosion resistant coating for a magnesium alloy surface as set forth in claim 1, wherein: in the step (3), the surface of the substrate is subjected to sand blasting treatment before cold spraying, surface oxides are removed, and the surface roughness Ra is 1.6-3.2 mu m after sand blasting treatment.
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