Anti-corrosion heat-dissipation graphene composite nano ceramic coating for magnesium alloy and preparation method and application of anti-corrosion heat-dissipation graphene composite nano ceramic coating

Abstract

The invention belongs to the technical field of graphene coatings, and particularly relates to an anti-corrosion heat dissipation graphene composite nano ceramic coating for magnesium alloy and a preparation method and application of the anti-corrosion heat dissipation graphene composite nano ceramic coating. A compact anti-corrosion heat-dissipation graphene composite nano-ceramic coating is constructed on the surface of the magnesium alloy by taking nano-deposition liquid as a raw material through a nano-deposition process, flaky graphene is coated with nano-ceramics in the coating to form a composite material, the composite material is orderly and directionally arranged on the surface of the magnesium alloy, and the anti-corrosion heat-dissipation graphene composite nano-ceramic coating is prepared through vapor deposition under the control of a matched magnetic field. And the compactness of the coating is further improved. According to the coating, the graphene is used as a main material, the coating is endowed with excellent corrosion resistance and heat dissipation performance through effective combination of the graphene and the nano ceramic, and the requirement for integration of full-coating covering and corrosion resistance and heat dissipation of magnesium alloy complex structures (such as pipes, threads, narrow spaces and the like) can be met.

Description

Technical Field

[0001] This invention relates to the field of graphene coating technology, and in particular to a corrosion-resistant and heat-dissipating graphene composite nano-ceramic coating for magnesium alloys, its preparation method, and its application. Background Technology

[0002] Magnesium alloys, as lightweight metallic materials, are widely used in aerospace, automotive, electronics and other fields. As a result, the requirements for the corrosion resistance and heat dissipation performance of magnesium alloys are becoming increasingly stringent. However, the inadequacy of the corrosion resistance and heat dissipation performance of traditional magnesium alloys has become a key bottleneck restricting their performance.

[0003] Traditional anti-corrosion coatings (such as electrophoretic coating and powder coating) can provide some corrosion protection, but the resulting coatings suffer from poor density and short anti-corrosion duration, with neutral salt spray tests lasting only tens of hours, making them unsuitable for demanding applications. Traditional heat dissipation coatings also struggle to simultaneously meet the requirements of full coverage and integrated corrosion protection and heat dissipation for complex structures (such as inside pipes, threads, and confined spaces).

[0004] Therefore, providing a new magnesium alloy coating that can meet the requirements of integrated corrosion protection and heat dissipation, has a dense structure, and is suitable for complex structures, as well as its preparation method, is an urgent problem to be solved. Summary of the Invention

[0005] The purpose of this invention is to provide a corrosion-resistant and heat-dissipating graphene composite nano-ceramic coating for magnesium alloys, its preparation method and application, to solve the above-mentioned problems existing in the existing corrosion-resistant or heat-dissipating coatings for magnesium alloys.

[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0007] This invention provides a method for preparing a corrosion-resistant and heat-dissipating graphene composite nano-ceramic coating for magnesium alloys, comprising the following steps:

[0008] (1) Magnesium alloy is magnetized to obtain a pretreated substrate;

[0009] (2) Under the control of a matching magnetic field, the pretreated substrate is subjected to liquid-phase nano-deposition in an anti-corrosion and heat dissipation nano-deposition liquid to obtain a substrate with a deposited composite coating.

[0010] (3) Under the condition of matching magnetic field control, the substrate with the deposited composite coating is purified in water to obtain the substrate with magnetic field controlled composite coating.

[0011] (4) Under the control of a matching magnetic field, the substrate of the magnetic field-controlled composite coating is rearranged under normal pressure and heating to obtain the substrate of the rearranged composite coating.

[0012] (5) Under the control of a matching magnetic field, a protective atmosphere is introduced, and the substrate of the rearranged composite coating is vapor-phase nano-deposited using an anti-corrosion and heat-dissipating nano-deposit liquid under normal pressure and heating to obtain an anti-corrosion and heat-dissipating graphene composite nano-ceramic coating for magnesium alloys.

[0013] Preferably, the anti-corrosion and heat dissipation nano-deposition liquid comprises the following raw materials in parts by weight:

[0014] 1-3 parts aluminum oxide, 0.1-10 parts silicon dioxide, 0.1-2 parts zirconium oxide, 1-10 parts silicon carbide, 1-3 parts boron nitride, 5-20 parts epoxy resin, 5-20 parts graphene, 1-5 parts magnetoelectric ion composite agent, 0.1-3 parts coupling agent, 0.1-1 part leveling agent, 0.1-1 part dispersant, 0.1-1 part wetting agent, 0.1-2 parts defoamer, and 120-300 parts water.

[0015] Preferably, the magnetoelectric ion composite agent is one or more of [bmim]FeCl4, [bpy]FeCl4, [bmp]FeCl4, and [pbmim](FeCl4)2.

[0016] Preferably, the preparation method of the corrosion-resistant and heat-dissipating nano-deposition liquid includes the following steps:

[0017] Graphene, aluminum oxide, silicon dioxide, boron nitride, silicon carbide, zirconium oxide, epoxy resin, coupling agent, defoamer, and water are mixed and aged to obtain an aging solution.

[0018] A magnetoelectric ion composite agent, leveling agent, dispersant, and wetting agent are added to the curing solution, and then ground and dispersed to obtain an anti-corrosion and heat dissipation nano-deposition solution.

[0019] Preferably, the curing temperature is 25–60°C, and the curing time is 12–48 hours.

[0020] Preferably, the liquid phase nanodeposition time in step (2) is 0.5 to 4 hours; and the gas phase nanodeposition time in step (5) is 0.5 to 8 hours.

[0021] Preferably, the matching magnetic field control in steps (2) to (5) refers to the matching of the magnetic field applied in steps (2) to (5) with the magnetic field of the pretreated substrate; the magnetic field force of the matching magnetic field control in steps (2) to (5) is independently 5 to 200 N.

[0022] The present invention also provides a corrosion-resistant and heat-dissipating graphene composite nano-ceramic coating for magnesium alloys prepared by the above preparation method.

[0023] The present invention also provides an application of a corrosion-resistant and heat-dissipating graphene composite nano-ceramic coating for magnesium alloys in magnesium alloy coatings.

[0024] As can be seen from the above technical solution, compared with the prior art, the present invention has the following beneficial effects:

[0025] This invention utilizes a nano-deposition process, using a nano-deposition liquid as a raw material, to construct a dense, corrosion-resistant, and heat-dissipating graphene composite nano-ceramic coating on the surface of magnesium alloys. The coating consists of nano-ceramics encapsulating sheet-like graphene to form a composite material, which is orderly and oriented on the magnesium alloy surface. Furthermore, the density of the coating is increased through vapor deposition under a matched magnetic field. The coating of this invention is primarily composed of graphene, and its effective combination with nano-ceramics endows the coating with excellent corrosion resistance and heat dissipation performance. It can meet the requirements for full coating coverage and integrated corrosion resistance and heat dissipation for complex magnesium alloy structures (such as inside pipes, threads, and confined spaces), and can be widely applied in aerospace, automotive, electronics, drones, aircraft, and submarines. Detailed Implementation

[0026] This invention provides a method for preparing a corrosion-resistant and heat-dissipating graphene composite nano-ceramic coating for magnesium alloys, comprising the following steps:

[0027] (1) Magnesium alloy is magnetized to obtain a pretreated substrate;

[0028] (2) Under the control of a matching magnetic field, the pretreated substrate is subjected to liquid-phase nano-deposition in an anti-corrosion and heat dissipation nano-deposition liquid to obtain a substrate with a deposited composite coating.

[0029] (3) Under the condition of matching magnetic field control, the substrate with the deposited composite coating is purified in water to obtain the substrate with magnetic field controlled composite coating.

[0030] (4) Under the control of a matching magnetic field, the substrate of the magnetic field-controlled composite coating is rearranged under normal pressure and heating to obtain the substrate of the rearranged composite coating.

[0031] (5) Under the control of a matching magnetic field, a protective atmosphere is introduced, and the substrate of the rearranged composite coating is vapor-phase nano-deposited using an anti-corrosion and heat-dissipating nano-deposit liquid under normal pressure and heating to obtain an anti-corrosion and heat-dissipating graphene composite nano-ceramic coating for magnesium alloys.

[0032] In this invention, the anti-corrosion and heat dissipation nano-deposition liquid comprises the following raw materials in parts by weight:

[0033] 1-3 parts aluminum oxide, 0.1-10 parts silicon dioxide, 0.1-2 parts zirconium oxide, 1-10 parts silicon carbide, 1-3 parts boron nitride, 5-20 parts epoxy resin, 5-20 parts graphene, 1-5 parts magnetoelectric ion composite agent, 0.1-3 parts coupling agent, 0.1-1 part leveling agent, 0.1-1 part dispersant, 0.1-1 part wetting agent, 0.1-2 parts defoamer, and 120-300 parts water.

[0034] In this invention, the epoxy resin is preferably F-44 and / or E-51, and more preferably E-51.

[0035] In this invention, the magnetoelectric ion composite agent is preferably one or more of [bmim]FeCl4, [bpy]FeCl4, [bmp]FeCl4, and [pbmim](FeCl4)2, more preferably [bmim]FeCl4 or [bpy]FeCl4, and even more preferably [bmim]FeCl4.

[0036] In this invention, the coupling agent is preferably a silane coupling agent and / or a titanate coupling agent, more preferably a silane coupling agent, and even more preferably KH550 or KH560.

[0037] In this invention, the leveling agent is preferably TEGO Wet 270 or TEGO Wet 280, and more preferably TEGO Wet 270.

[0038] In this invention, the dispersant is preferably sodium polyacrylate and / or ammonium polyacrylate, more preferably ammonium polyacrylate.

[0039] In this invention, the wetting agent is preferably alkylphenol polyoxyethylene ether.

[0040] In this invention, the defoamer is preferably one or more of BYK-017, BYK-019, and BYK-044, more preferably BYK-017 or BYK-019, and even more preferably BYK-017.

[0041] In this invention, the preparation method of the anti-corrosion and heat dissipation nano-deposition liquid includes the following steps:

[0042] Graphene, aluminum oxide, silicon dioxide, boron nitride, silicon carbide, zirconium oxide, epoxy resin, coupling agent, defoamer, and water are mixed and aged to obtain an aging solution.

[0043] A magnetoelectric ion composite agent, leveling agent, dispersant, and wetting agent are added to the curing solution, and then ground and dispersed to obtain an anti-corrosion and heat dissipation nano-deposition solution.

[0044] In this invention, the curing temperature is preferably 25-60°C, more preferably 40-55°C, and even more preferably 50°C; the curing time is preferably 12-48h, more preferably 24-42h, and even more preferably 36h.

[0045] In this invention, the particle size after grinding and dispersing is preferably 1 to 2 μm, more preferably 1.5 to 2 μm, and even more preferably 2 μm.

[0046] In this invention, the magnetization process in step (1) refers to magnetization using a magnetizer; the magnetization voltage is preferably 100-500V, more preferably 200-400V, and even more preferably 220V; the magnetization temperature is preferably 25℃; the magnetization time is preferably 1-30s, more preferably 10-20s, and even more preferably 20s.

[0047] In this invention, the matching magnetic field control in steps (2) to (5) refers to the matching of the magnetic field applied in steps (2) to (5) with the magnetic field of the pretreated substrate; the magnetic field force of the matching magnetic field control in steps (2) to (5) is preferably 5 to 200 N, more preferably 70 to 150 N, and more preferably 120 N.

[0048] In this invention, the liquid phase nanodeposition time in step (2) is preferably 0.5 to 4 hours, more preferably 1 to 3 hours, and even more preferably 2 hours.

[0049] In this invention, the time for removing impurities in step (3) is preferably 30 to 60 minutes, more preferably 40 to 50 minutes, and even more preferably 50 minutes.

[0050] In this invention, the re-arrangement time in step (4) is preferably 1 to 3 hours, more preferably 1 to 2 hours, and even more preferably 2 hours.

[0051] In this invention, the vapor-phase nanodeposition time in step (5) is preferably 0.5 to 8 hours, more preferably 2 to 6 hours, and even more preferably 3 hours.

[0052] In this invention, the protective atmosphere in step (5) is preferably argon.

[0053] In this invention, the temperature of the atmospheric pressure heating in step (4) is preferably 100-200°C, more preferably 120-180°C, and even more preferably 160°C.

[0054] In this invention, the temperature of the atmospheric pressure heating in step (5) is preferably 100-200°C, more preferably 150-200°C, and even more preferably 200°C.

[0055] The present invention also provides a corrosion-resistant and heat-dissipating graphene composite nano-ceramic coating for magnesium alloys prepared by the above preparation method.

[0056] The present invention also provides an application of a corrosion-resistant and heat-dissipating graphene composite nano-ceramic coating for magnesium alloys in magnesium alloy coatings.

[0057] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0058] Example 1

[0059] The preparation method of the anti-corrosion and heat dissipation graphene composite nano-ceramic coating for magnesium alloys includes the following steps:

[0060] (1) Magnesium alloy was magnetized for 20 seconds at 220V using a magnetizer to obtain a pretreated substrate;

[0061] (2) Apply a magnetic field that matches the magnetic field of the pretreated substrate. Under the condition of magnetic field force of 120N, place the pretreated substrate in the anti-corrosion and heat dissipation nano deposition liquid for liquid phase nano deposition. The deposition is completed after 2 hours to obtain the substrate with the deposited composite coating.

[0062] (3) Place the substrate with the deposited composite coating in water, match the magnetic field applied to the water with the magnetic field of the pretreated substrate, and remove impurities for 50 minutes under a magnetic field force of 80N to obtain a substrate with a magnetic field controlled composite coating.

[0063] (4) Apply a magnetic field that matches the magnetic field of the pretreated substrate, and heat the substrate of the magnetic field-controlled composite coating to 160°C under normal pressure for 2 hours under a magnetic field force of 120N to obtain the substrate of the rearranged composite coating.

[0064] (5) Apply a magnetic field that matches the magnetic field of the pretreated substrate. Under the condition of magnetic field force of 120N, argon gas is introduced and nano-deposition slurry is vapor-deposited on the substrate of the rearranged composite coating at atmospheric pressure and heated to 200℃. After deposition for 3h, a graphene composite nano-ceramic coating with a thickness of 58μm for corrosion protection and heat dissipation of magnesium alloy is obtained.

[0065] The corrosion-resistant and heat-dissipating nano-deposition liquid contains the following raw materials in parts by weight:

[0066] 3 parts aluminum oxide, 8 parts silicon dioxide, 0.3 parts zirconium oxide, 7 parts silicon carbide, 2 parts boron nitride, 8 parts epoxy resin E-511, 16 parts graphene, 4 parts magnetoelectric ion composite agent ([bmim]FeCl4), 2 parts coupling agent KH560, 0.3 parts leveling agent TEGOWet 270, 0.5 parts dispersant sodium polyacrylate, 0.2 parts wetting agent alkylphenol polyoxyethylene ether, 0.3 parts defoamer BYK-017, and 200 parts water.

[0067] A method for preparing an anti-corrosion and heat-dissipating nano-deposition liquid includes the following steps:

[0068] Graphene, aluminum oxide, silicon dioxide, boron nitride, silicon carbide, zirconium oxide, epoxy resin, coupling agent, defoamer, and water were stirred evenly and then aged at 50°C for 36 hours to obtain an aging solution. Magnetoelectric ion composite agent, leveling agent, dispersant, and wetting agent were added to the aging solution in sequence and stirred evenly. Then, the mixture was ground and dispersed to a particle size of 2μm to obtain an anti-corrosion and heat dissipation nano-deposition solution.

[0069] Example 2

[0070] The preparation method of the anti-corrosion and heat dissipation graphene composite nano-ceramic coating for magnesium alloy is described in Example 1. The difference is that the magnetic field force in steps (2) to (5) is 80N, the deposition time in step (2) is 1h, and the ambient pressure heating temperature in step (5) is 180℃ and the deposition time is 2h, so as to obtain an anti-corrosion and heat dissipation graphene composite nano-ceramic coating for magnesium alloy with a thickness of 43μm.

[0071] The corrosion-resistant and heat-dissipating nano-deposition liquid contains the following raw materials in parts by weight:

[0072] 1 part aluminum oxide, 5 parts silicon dioxide, 1 part zirconium oxide, 3 parts silicon carbide, 1 part boron nitride, 10 parts epoxy resin E-441, 12 parts graphene, 3 parts magnetoelectric ion composite agent ([bpy]FeCl4), 1 part coupling agent KH550, 0.5 parts leveling agent TEGO Wet280, 1 part dispersant ammonium polyacrylate, 0.1 part wetting agent alkylphenol polyoxyethylene ether, 0.5 parts defoamer BYK-019, and 260 parts water.

[0073] Comparative Example 1

[0074] The composition of a nano-deposition liquid is detailed in Example 1, except that it does not contain graphene.

[0075] For details on the preparation method of the nano-deposition liquid, please refer to Example 1. For details on the method of preparing a coating for magnesium alloy using the nano-deposition liquid, please refer to Example 1.

[0076] Comparative Example 2

[0077] The composition of a nano-deposition solution is described in Example 1, except that it does not contain aluminum oxide, silicon dioxide, boron nitride, silicon carbide, or zirconium oxide.

[0078] For details on the preparation method of the nano-deposition liquid, please refer to Example 1. For details on the method of preparing a coating for magnesium alloy using the nano-deposition liquid, please refer to Example 1.

[0079] The test results of the mechanical properties, corrosion resistance, and heat dissipation performance of the coatings of Examples 1-2 and Comparative Examples 1-2 are shown in Table 1.

[0080] Table 1 Performance test results of the coating

[0081]

[0082] As shown in Table 1, the coating prepared by the anti-corrosion and heat dissipation nano-deposition liquid of the present invention has good anti-corrosion and heat dissipation performance, and also has good adhesion, which can achieve good adhesion to the magnesium alloy substrate.

[0083] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing a corrosion-resistant and heat-dissipating graphene composite nano-ceramic coating for magnesium alloys, characterized in that, Includes the following steps: (1) Magnesium alloy is magnetized to obtain a pretreated substrate; (2) Under the control of a matching magnetic field, the pretreated substrate is subjected to liquid-phase nano-deposition in an anti-corrosion and heat dissipation nano-deposition liquid to obtain a substrate with a deposited composite coating. (3) Under the condition of matching magnetic field control, the substrate with the deposited composite coating is purified in water to obtain the substrate with magnetic field controlled composite coating. (4) Under the control of a matching magnetic field, the substrate of the magnetic field-controlled composite coating is rearranged under normal pressure and heating to obtain the substrate of the rearranged composite coating. (5) Under the control of a matching magnetic field, a protective atmosphere is introduced, and the substrate of the rearranged composite coating is vapor-phase nano-deposited using an anti-corrosion and heat-dissipating nano-deposit liquid under normal pressure and heating to obtain an anti-corrosion and heat-dissipating graphene composite nano-ceramic coating for magnesium alloy. The corrosion-resistant and heat-dissipating nano-deposition liquid contains the following raw materials in parts by weight: 1-3 parts aluminum oxide, 0.1-10 parts silicon dioxide, 0.1-2 parts zirconium oxide, 1-10 parts silicon carbide, 1-3 parts boron nitride, 5-20 parts epoxy resin, 5-20 parts graphene, 1-5 parts magnetoelectric ion composite agent, 0.1-3 parts coupling agent, 0.1-1 part leveling agent, 0.1-1 part dispersant, 0.1-1 part wetting agent, 0.1-2 parts defoamer, and 120-300 parts water.

2. The preparation method according to claim 1, characterized in that, The magnetoelectric ion composite agent is one or more of [bmim]FeCl4, [bpy]FeCl4, [bmp]FeCl4, and [pbmim](FeCl4)2.

3. The preparation method according to claim 2, characterized in that, The preparation method of the corrosion-resistant and heat-dissipating nano-deposition liquid includes the following steps: Graphene, aluminum oxide, silicon dioxide, boron nitride, silicon carbide, zirconium oxide, epoxy resin, coupling agent, defoamer, and water are mixed and aged to obtain an aging solution. A magnetoelectric ion composite agent, leveling agent, dispersant, and wetting agent are added to the curing solution, and then ground and dispersed to obtain an anti-corrosion and heat dissipation nano-deposition solution.

4. The preparation method according to claim 3, characterized in that, The curing temperature is 25–60°C; the curing time is 12–48 hours.

5. The preparation method according to claim 1, characterized in that, The liquid phase nanodeposition time in step (2) is 0.5 to 4 hours; the gas phase nanodeposition time in step (5) is 0.5 to 8 hours.

6. The preparation method according to claim 5, characterized in that, The matching magnetic field control in steps (2) to (5) refers to the matching of the magnetic field applied in steps (2) to (5) with the magnetic field of the pretreated substrate; the magnetic field force of the matching magnetic field control in steps (2) to (5) is independently 5 to 200 N.

7. A corrosion-resistant and heat-dissipating graphene composite nano-ceramic coating for magnesium alloys prepared by the preparation method according to any one of claims 1 to 6.

8. The application of the anti-corrosion and heat dissipation graphene composite nano-ceramic coating for magnesium alloys as described in claim 7 in magnesium alloy coatings.

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