High-thermal-conductivity durable anticorrosive nanocoating and preparation method thereof

Abstract

The application provides a high-thermal-conductivity durable anticorrosion nanometer coating, which comprises the following components in proportion by mass: 60-80 parts of a solvent; 60-70 parts of an epoxy resin; 0.5-5 parts of three-dimensional graphene aerogel; 5-10 parts of a curing agent; 5-15 parts of zero-dimensional nanometer diamond; and 1-10 parts of carbon nanotube loaded Co-doped CeO2 / TiO2 composite material; the three-dimensional graphene aerogel formed by the zero-dimensional diamond, one-dimensional carbon nanotube and two-dimensional graphene nanosheet assembles a "point-line-surface-body" synergistic thermal conduction network, and the carbon nanotube loaded Co-doped CeO2 / TiO2 nanosheet composite material endows the coating with excellent antibacterial property and ultraviolet aging resistance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of functional coating of metal surface, and particularly relates to a multifunctional coating for the surface of a heat sink, which has high heat dissipation, excellent corrosion resistance and anti-ultraviolet aging performance, and a preparation method thereof. BACKGROUND

[0002] As a core component of active or passive heat dissipation systems, heat sinks are widely used in key fields such as electronic communication, automobile industry, aerospace and power conversion equipment. The core function of the heat sink is to dissipate the heat generated during the operation of the device to the environment efficiently, thereby ensuring that the core components work stably at a safe temperature. The performance of the heat sink directly determines the reliability, efficiency and service life of the entire system. However, with the continuous improvement of device power density and the increasing severity of application environment, the heat dissipation requirements of the heat sink are continuously increasing. In order to improve the heat dissipation efficiency, the existing research coats the heat dissipation coating on the surface of the heat sink to improve the surface radiation efficiency and enhance the heat dissipation performance. In addition, the heat dissipation coating can also increase the self-cleaning, insulating, corrosion-resistant and other properties while reducing the temperature.

[0003] Patent document CN120248731A discloses a heat dissipation coating composition. Specifically, methyl methacrylate, 2-vinylpyridine, methacrylamide, dipropylene glycol diacrylate, azobisisobutyronitrile and tetradecane are used as raw materials to prepare a coating dispersion liquid. Then, based on the in-situ polymerization method, the coating dispersion liquid is used to polymerize and coat the hydroxylated graphene to construct a coating layer with amino and pyridine ring, thereby obtaining coated particles. Then, the coated particles are combined with boron nitride amino by using glycol diglycidyl ether containing double-end epoxy groups as a bridging agent through the addition of amino and epoxy groups. The modified composite particles are prepared, and the heat dissipation coating composition is prepared by blending the modified composite particles with water-based epoxy resin and other components. The heat dissipation coating composition has excellent heat dissipation performance. CN120718507A discloses that the heat dissipation of the heat dissipation type corrosion-resistant coating is improved by introducing heat-conducting water-based epoxy resin, graphene and functionalized boron nitride microspheres into the heat dissipation coating. At the same time, by introducing graphene and functionalized boron nitride microspheres, the micro defects in the water-based epoxy coating are effectively plugged, and the diffusion path of the corrosion medium in the coating is prolonged, i.e. the "labyrinth effect", thereby improving the corrosion resistance of the heat dissipation type corrosion-resistant coating. However, the preparation process of the above heat dissipation coating is complex, the synergistic effect between the heat dissipation components is not considered, and the coating is prone to problems such as powdering, discoloration, loss of luster, embrittlement and cracking when exposed to sunlight and ultraviolet light for a long time. SUMMARY

[0004] In view of the above technical problems, the present application provides a nano coating and a preparation method thereof, which can simultaneously improve the heat dissipation performance, corrosion resistance and anti-ultraviolet aging ability of the heat sink.

[0005] The high-thermal-conductivity durable anticorrosion nanocoating comprises the following components in proportion by mass: 60-80 parts of solvent; 60-70 parts of epoxy resin; 0.5-5 parts of three-dimensional graphene aerogel; 5-10 parts of curing agent; 5-15 parts of zero-dimensional nanodiamond; and 1-10 parts of carbon nanotube loaded Co-doped CeO2 / TiO2 composite material.

[0006] The preparation process of the carbon nanotube loaded Co-doped CeO2 / TiO2 is as follows:

[0007] (1) The carbon nanotubes are subjected to acidification treatment, washing and drying, and are dispersed in deionized water to form a black dispersion liquid; cerium source, titanium source, cobalt-doped element source and ethylenediamine are added into the dispersion liquid, and are stirred for 10-30 min to be uniformly mixed;

[0008] (2) The uniformly mixed solution is transferred into an autoclave, and is reacted at 180-210 DEG C for 10-20 h; after the reaction, the product is washed and dried;

[0009] (3) The product of step (2) is heat-treated at 300-400 DEG C for 1-2 h in an inert atmosphere to obtain a one-dimensional carbon nanotube loaded Co-doped CeO2 / TiO2 nanosheet composite material.

[0010] In a specific embodiment, the three-dimensional graphene aerogel is prepared by a hydrothermal method.

[0011] In a specific embodiment, the curing agent is selected from one or more of hydroxyalkyl amide, succinic anhydride, hexanediamine and diethylenetriamine;

[0012] In a specific embodiment, the solvent is acetone or ethanol;

[0013] In a specific embodiment, the cerium source is cerium nitrate hexahydrate, the titanium source is tetrabutyl titanate, and the cobalt source is cobalt nitrate or cobalt sulfate; the molar ratio of the cerium source, the titanium source, the cobalt source and ethylenediamine is 1:(0.5-2):(0.05-0.3):(3-5);

[0014] In a specific embodiment, the epoxy resin is bisphenol A type epoxy resin.

[0015] In a specific embodiment, the epoxy resin, the three-dimensional graphene aerogel, the curing agent, the zero-dimensional nanodiamond and the carbon nanotube loaded Co-doped CeO2 / TiO2 composite material are sequentially added into the solvent, and are stirred for 1-2 h to be uniformly mixed, so that the high-thermal-conductivity durable anticorrosion nanocoating is obtained.

[0016] Compared with the prior art, the application can achieve the following technical effects:

[0017] (1) This application utilizes a three-dimensional graphene aerogel assembled from zero-dimensional diamond, one-dimensional carbon nanotubes, and two-dimensional graphene nanosheets to form a synergistic thermal conductive network of "point-line-surface-volume". The one-dimensional carbon nanotubes serve as high-speed thermal conductive pathways, forming ultra-long thermal conductive paths for rapid heat transfer. The three-dimensional thermally conductive graphene formed by the two-dimensional nanosheets forms a three-dimensional thermal conductive network, providing a huge thermally conductive specific surface area and enhancing the heat exchange efficiency with the external environment. Zero-dimensional nanodiamonds fill the spaces between the carbon nanotubes and graphene sheets, effectively acting as thermal bridges and improving the density of the thermal conductive network. The growth of Co-doped CeO2 / TiO2 nanosheets on the carbon nanotubes can improve the surface roughness of the coating and further enhance the heat dissipation performance. In addition, the growth of Co-doped CeO2 / TiO2 nanosheets on the carbon nanotubes and the addition of nanodiamonds directly improve the coating hardness.

[0018] (2) The growth of Co-doped CeO2 / TiO2 nanosheets on carbon nanotubes not only avoids the aggregation of carbon nanotubes, but also provides an attachment surface for the Co-doped CeO2 / TiO2 nanosheets with the one-dimensional structure of CNTs, allowing them to be loaded on them in a highly dispersed manner, thus easily exposing more active sites. Co doping effectively broadens the ultraviolet absorption range of CeO2 / TiO2 and improves the scattering and absorption efficiency of ultraviolet light. CNTs can promote the conduction of photogenerated electrons and greatly suppress electron-hole recombination.

[0019] (3) The composite material of Co-doped CeO2 / TiO2 nanosheets grown on carbon nanotubes also has excellent antibacterial properties. Adding it to heat dissipation coating greatly improves its self-cleaning and corrosion resistance.

[0020] (4) The coating is made of carefully selected functional materials of different dimensions. The different materials work together to give the nano coating excellent heat dissipation, corrosion prevention and UV protection.

[0021] (5) The heat dissipation coating has a simple preparation process and can be applied to various types of heat exchangers, such as air-cooled / liquid-cooled heat exchangers for data centers, cooling modules for energy storage and battery thermal management systems, industrial cooling towers, ships, and high-speed rail heat exchangers. Attached Figure Description

[0022] Appendix Figure 1 This is a SEM image of the Co-doped TiO2 / CeO2 nanosheet composite material grown on carbon nanotubes in this application. Detailed Implementation

[0023] In order to make the technical solutions of the present application clearer, the present application will be further described below in combination with embodiments. For those skilled in the art, other equivalent alternative solutions can also be obtained without creative labor on the basis of these embodiments, and all of them shall fall within the protection scope of the present application.

[0024] Embodiment 1

[0025] According to the mass ratio, 60 parts of bisphenol A type epoxy resin, 3 parts of three-dimensional graphene aerogel material, 7 parts of curing agent hexamethylene diamine, 10 parts of zero-dimensional nanometer diamond and 8 parts of carbon nanotube loaded Co-doped CeO2 / TiO2 were sequentially added in 60 parts of acetone solvent, and stirred for 1 h to obtain a heat dissipation coating.

[0026] The preparation process of the carbon nanotube loaded Co-doped CeO2 / TiO2 is specifically as follows:

[0027] (1) 30 mg of carbon nanotubes were acidized by concentrated nitric acid, washed, dried, and dispersed in 80 ml of deionized water to form a black dispersion liquid; 3 mmol of cerium nitrate hexahydrate, 3 mmol of tetrabutyl titanate, 0.2 mmol of cobalt nitrate and 10 mmol of ethylenediamine were added to the dispersion liquid, and stirred for 20 min to mix uniformly; (2) the uniformly mixed solution was transferred to an autoclave, and reacted at 180℃ for 10 h; after the reaction was completed, the product was washed and dried; (3) the product of step (2) was heat-treated at 300℃ for 1 h under a nitrogen atmosphere to obtain a one-dimensional carbon nanotube loaded Co-doped CeO2 / TiO2 nanosheet composite material.

[0028] Embodiment 2

[0029] According to the mass ratio, 60 parts of bisphenol A type epoxy resin, 3 parts of three-dimensional graphene aerogel material, 7 parts of curing agent hexamethylene diamine, 10 parts of zero-dimensional nanometer diamond and 8 parts of carbon nanotube loaded Co-doped CeO2 / TiO2 were sequentially added in 60 parts of acetone solvent, and stirred for 1 h to obtain a heat dissipation coating.

[0030] The preparation process of the carbon nanotube loaded Co-doped CeO2 / TiO2 is specifically as follows:

[0031] (1) 40 mg carbon nanotubes were acidized with concentrated nitric acid, washed, dried, and dispersed in 80 ml of deionized water to form a black dispersion liquid; 3 mmol of cerium nitrate hexahydrate, 3 mmol of tetrabutyl titanate, and 0.3 mmol of cobalt nitrate and 12 mmol of ethylenediamine were added to the dispersion liquid, stirred for 20 min, and mixed uniformly; (2) the uniformly mixed solution was transferred to an autoclave, reacted at 190°C for 10 h, and after the reaction was completed, washed and dried; (3) the product of step (2) was heat-treated at 350°C for 1 h under a nitrogen atmosphere to obtain a one-dimensional carbon nanotube loaded Co-doped CeO2 / TiO2 nanosheet composite material.

[0032] Comparative Example 1

[0033] According to the mass ratio, 60 parts of bisphenol A type epoxy resin, 3 parts of three-dimensional graphene aerogel material, 7 parts of curing agent ethylenediamine, and 10 parts of zero-dimensional nanodiamond were sequentially added to 60 parts of acetone solvent, stirred for 1 h to mix uniformly, and a coating was obtained.

[0034] Comparative Example 2

[0035] According to the mass ratio, 60 parts of bisphenol A type epoxy resin, 7 parts of curing agent ethylenediamine, and 10 parts of zero-dimensional nanodiamond were sequentially added to 60 parts of acetone solvent, stirred for 1 h to mix uniformly, and a coating was obtained.

[0036] The preparation process of the carbon nanotube loaded Co-doped CeO2 / TiO2 is as follows:

[0037] (1) 30 mg of carbon nanotubes were acidized with concentrated nitric acid, washed, dried, and dispersed in 80 ml of deionized water to form a black dispersion liquid; 3 mmol of cerium nitrate hexahydrate, 3 mmol of tetrabutyl titanate, and 0.2 mmol of cobalt nitrate and 10 mmol of ethylenediamine were added to the dispersion liquid, stirred for 20 min, and mixed uniformly; (2) the uniformly mixed solution was transferred to an autoclave, reacted at 180°C for 10 h, and after the reaction was completed, washed and dried; (3) the product of step (2) was heat-treated at 300°C for 1 h under a nitrogen atmosphere to obtain a one-dimensional carbon nanotube loaded Co-doped CeO2 / TiO2 nanosheet composite material.

[0038] Comparative Example 3

[0039] According to the mass ratio, 60 parts of bisphenol A type epoxy resin, 3 parts of three-dimensional graphene aerogel material, 7 parts of curing agent ethylenediamine, and 8 parts of carbon nanotube loaded Co-doped CeO2 / TiO2 were sequentially added to 60 parts of acetone solvent, stirred for 1 h to mix uniformly, and a coating was obtained.

[0040] The preparation process of the carbon nanotube loaded Co-doped CeO2 / TiO2 is as follows:

[0041] (1) 30 mg of carbon nanotubes were acidized by concentrated nitric acid, washed, dried, and dispersed in 80 ml of deionized water to form a black dispersion liquid; 3 mmol of cerium nitrate hexahydrate, 3 mmol of tetrabutyl titanate, and 0.2 mmol of cobalt nitrate were added to the dispersion liquid, and 10 mmol of ethylenediamine was added, and stirred for 20 min to mix uniformly; (2) the uniformly mixed solution was transferred to an autoclave, and reacted at 180°C for 10 h; after the reaction was completed, the product was washed and dried; (3) the product of step (2) was heat-treated at 300°C for 1 h under a nitrogen atmosphere to obtain a one-dimensional carbon nanotube loaded Co-doped CeO2 / TiO2 nanosheet composite material.

[0042] The antibacterial properties of the coatings of Examples 1-2 and Comparative Examples 1-3 were tested according to HG / T 3950-2007.

[0043] The coatings prepared in Examples 1-2 and Comparative Examples 1-3 were coated on the surface of a stainless steel plate with a size of 50 mm x 50 mm x 5 mm, and after curing treatment, a coating layer with a thickness of 80 μm was formed. The thermal conductivity of the coating layer (unit: W / m·K) was tested; the pencil hardness of the coating layer was tested according to GB / T 6739-2022; after the test was completed, it was placed in an ultraviolet aging test box, the test temperature was set to 60°C, the irradiation power was 300W, and after 3000h of storage, the surface state of the coating layer was observed.

[0044] The test results are shown in Table 1. The coating of Example 1-2 showed obvious advantages in thermal conductivity, antibacterial property, ultraviolet aging resistance, and pencil hardness.

[0045] Table 1

[0046]

[0047] Finally, it should be noted that the above description is only a preferred embodiment of the present application and is not intended to limit the present application. Although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent replacements to some technical features. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A high thermal conductive, durable, anticorrosive nanocoating, characterized in that, According to the mass proportion, it comprises the following components: 60-80 parts of solvent; 60-70 parts of epoxy resin; 0.5-5 parts of three-dimensional graphene aerogel; 5-10 parts of curing agent; 5-15 parts of zero-dimensional nanodiamond; 1-10 parts of carbon nanotube loaded Co-doped CeO2 / TiO2 composite material; The preparation process of the carbon nanotube loaded Co-doped CeO2 / TiO2 is as follows: (1) The carbon nanotubes are acidified, washed, dried, and dispersed in deionized water to form a black dispersion liquid; cerium source, titanium source, and doped element cobalt source and ethylenediamine are added to the dispersion liquid, stirred for 10-30 min, and mixed uniformly; (2) The mixed uniform solution is transferred to an autoclave, reacted at 180-210°C for 10-20h, and after the reaction is completed, washed and dried; (3) The product of step (2) is heat treated at 300-400°C for 1-2h under an inert atmosphere to obtain a one-dimensional carbon nanotube loaded Co-doped CeO2 / TiO2 nanosheet composite material.

2. The high thermal conductive durable anticorrosive nanocoating according to claim 1, characterized in that, The three-dimensional graphene aerogel is prepared by a hydrothermal method.

3. The high thermal conductive durable anticorrosive nanocoating according to claim 1, characterized in that, The curing agent is selected from one or more of hydroxyalkyl amide, succinic anhydride, hexanediamine, and diethylenetriamine.

4. The high thermal conductive durable anticorrosive nanocoating according to claim 1, characterized in that, The solvent is acetone or ethanol.

5. The high thermal conductive durable anticorrosive nanocoating according to claim 1, characterized in that, The cerium source is cerium nitrate hexahydrate, the titanium source is tetrabutyl titanate, the cobalt source is cobalt nitrate or cobalt sulfate, and the molar ratio of the cerium source, titanium source, cobalt source, and ethylenediamine is 1:(0.5-2):(0.05-0.2):(3-5).

6. The high thermal conductive durable anticorrosive nanocoating according to claim 1, characterized in that, The epoxy resin is bisphenol A type epoxy resin.

7. A method for preparing the high thermal conductive durable anticorrosive nanocoating as claimed in any one of claims 1 to 6, characterized in that, In the solvent, the epoxy resin, three-dimensional graphene aerogel, curing agent, zero-dimensional nanodiamond, and carbon nanotube loaded Co-doped CeO2 / TiO2 composite material are added in sequence, stirred for 1-2h to mix uniformly, and a high-thermal-conductivity durable anticorrosive nanocoating is obtained.

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