Solvent type graphene nano ceramic coating

Abstract

The invention discloses a solvent type graphene nano ceramic coating which is formed by mixing a curing agent and a main agent according to the ratio of 1: (3-6), the main agent is prepared from flexible epoxy resin, a diluent, graphene nanosheets, spherical aluminum oxide, zinc powder, mica powder, a silane coupling agent, fumed silica and an additive; the curing agent is a modified amine curing agent. Flaky graphene is used as a main filler to construct a two-dimensional heat-conducting path, spherical aluminum oxide is used as an auxiliary material to construct a three-dimensional heat-conducting network to improve the heat-conducting capacity of the ceramic coating, the material flexibility can be kept through the sphere shape, and zinc powder and mica powder are added as an auxiliary material to improve the corrosion resistance.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of paint, in particular to a solvent type graphene nanoceramic paint. BACKGROUND

[0002] Coolers are one of the necessary equipment when the ship sails on the sea, since the sea water source is easy to obtain and low cost, it is often used as a cooling medium. But the main technical problem faced by the sea water cooler is the corrosion problem, the high salt content and chloride ion of sea water have strong corrosiveness to common heat-conducting materials such as carbon steel and ordinary copper alloy, therefore, after a period of use, it will cause serious corrosion of the parts of the sea water cooler, increase the use and maintenance cost, and shorten the service life of the equipment. If the cooler using corrosion-resistant materials (such as titanium pipe) is used, but the cost is high.

[0003] Therefore, using low-cost conventional metal materials and auxiliary heat transfer corrosion-resistant paint has become the subject of research in the field. But in the prior art, the general ceramic paint cannot consider both the heat transfer capacity and the corrosion resistance, although it can prolong the service life of the cooler, but it still cannot resist the long-term corrosion of sea water, and the heat conduction capacity and corrosion resistance cannot be considered.

[0004] Therefore, it is urgent to develop a paint for sea water coolers that can be used in long-term sea water immersion environment, protect the facilities and equipment from sea water erosion and can efficiently conduct heat, at the same time, the paint will not be affected by the thermal expansion of the base material and produce cracks. SUMMARY

[0005] Therefore, the purpose of the present application is to provide a solvent type graphene nanoceramic paint, which can be used in long-term sea water immersion environment for sea water coolers, protect the facilities and equipment from sea water erosion and can efficiently conduct heat, at the same time, the paint will not be affected by the thermal expansion of the base material and produce cracks.

[0006] The solvent type graphene nanoceramic paint of the present application is characterized in that: the curing agent and the main agent are mixed in a ratio of 1:3-6; the main agent is composed of flexible epoxy resin, diluent, graphene nanosheet, spherical alumina, zinc powder, mica powder, silane coupling agent, fumed silica and additive.

[0007] Further, the main agent is composed of 18-25% of flexible epoxy resin, 3-7% of diluent, 3-6% of graphene nanosheet, 30-40% of spherical alumina, 6-10% of zinc powder, 1-5% of mica powder, 1-2% of silane coupling agent and the rest of additive.

[0008] Further, the excess additive is composed of dispersant 1-4%, defoamer 0.3-0.6%, leveling agent 0.3-0.7%, fumed silica 0.5-1.5% and mixed solvent 15-20%, the percentage is the mass percentage of the main agent.

[0009] Further, the diluent is one or several of n-butyl glycidyl ether, isobutyl glycidyl ether and tert-butyl glycidyl ether; the silane coupling agent is one or several of methyl triethoxysilane, methyl tetramethoxysilane, methyl tetraethoxysilane, phenyl trimethoxysilane, diphenyl dimethoxysilane, methyl phenyl dimethoxysilane and gamma-(2,3-epoxypropoxy) propyl trimethoxysilane.

[0010] Further, the dispersant is one or several of BYK-2000 series, the defoamer is one or several of BYK-000 series, the leveling agent is one or several of BYK-300 series; the mixed solvent is propylene glycol methyl ether acetate and xylene, and the mixed solvent is mixed at a ratio of 1:1.

[0011] Further, the zinc powder and mica powder are both selected as 800 mesh sheet structure, the graphene nanosheet is multi-layer with a sheet diameter of 6-8 mu m; the flexible epoxy resin is selected as an epoxy equivalent of 550-800, and the elongation at break is greater than 30%.

[0012] Further, the curing agent is a modified amine curing agent.

[0013] Further, the main agent is composed of 20% flexible epoxy resin, 5% n-butyl glycidyl ether, 5% graphene nanosheet, 35% spherical alumina, 7% zinc powder, 3% mica powder and 1.5% gamma-(2,3-epoxypropoxy) propyl trimethoxysilane according to the mass percentage; the additive is selected as 3% BYK-2152, 0.5% BYK-052, 0.3% BYK-306 and 1% fumed silica; and the mixed solvent is selected as 18.7% propylene glycol methyl ether acetate and xylene mixed solution.

[0014] The present application has the following beneficial effects: the solvent type graphene nanoceramic coating of the present application uses sheet-shaped graphene as the main filler to construct a two-dimensional heat conduction path, and spherical alumina is used to construct a three-dimensional heat conduction network to improve the heat conduction capacity of the ceramic coating, and the spherical shape can also maintain the flexibility of the material, and sheet-shaped zinc powder and sheet-shaped mica powder are additionally added to improve the corrosion resistance. BRIEF DESCRIPTION OF DRAWINGS

[0015] The present application will be further described below in combination with the drawings and examples:

[0016] ATTACHMENT Fig. 1 The contrast statistical chart of the heat conductivity and corrosion resistance in different examples;

[0017] Figure 2 Fig. 2 Figure 3 DETAILED DESCRIPTION

[0018] Figure 1 Figs. 1-2 The present embodiment further illustrates a solvent-based graphene nanoceramic coating, which is characterized in that the solvent-based graphene nanoceramic coating is prepared by mixing a curing agent and a main agent in a ratio of 1:3-6; the main agent is composed of flexible epoxy resin, diluent, graphene nanosheet, spherical alumina, zinc powder, mica powder, silane coupling agent, fumed silica, and additive; the coating has good thermal conductivity and corrosion resistance to meet daily use.

[0019] In the present embodiment, the main agent is composed of 18-25% of flexible epoxy resin, 3-7% of diluent, 3-6% of graphene nanosheet, 30-40% of spherical alumina, 6-10% of zinc powder, 1-5% of mica powder, 1-2% of silane coupling agent, and the rest of additive; the flexible epoxy resin, as one of the base materials, mainly improves the flexibility of the ceramic coating, and the active diluent specifically regulates the viscosity and fluidity of the flexible epoxy resin; the graphene, as the main filler, constructs a two-dimensional thermal conduction path; the spherical alumina constructs a three-dimensional thermal conduction network to enhance the thermal conductivity; the two cooperate to conduct heat and provide basic corrosion resistance.

[0020] In the present embodiment, the rest of the additive is composed of 1-4% of dispersant, 0.3-0.6% of defoaming agent, 0.3-0.7% of leveling agent, 0.5-1.5% of fumed silica, and 15-20% of mixed solvent, which is the mass percentage of the main agent. The additives and solvents can help stabilize the chemical properties of the coating. The dispersant can help the functional groups formed by the graphene sheets to be evenly dispersed in the base material, constructing a uniform structure and maintaining good thermal conductivity; the fumed silica, as a very important and widely used functional nanomaterial, acts as a thixotropic anti-settling agent in the present embodiment, which can prevent settling during storage, prolong the service life, and reduce material loss.

[0021] In the present embodiment, the diluent is one or more of n-butyl glycidyl ether, isobutyl glycidyl ether, and tert-butyl glycidyl ether; the silane coupling agent is one or more of methyl triethoxysilane, methyl tetramethoxysilane, methyl tetraethoxysilane, phenyl trimethoxysilane, diphenyl dimethoxysilane, methyl phenyl dimethoxysilane, and γ-(2,3-epoxypropoxy) propyl trimethoxysilane; in the present embodiment, n-butyl glycidyl ether is selected, which is easy to obtain and reduces production cost; the silane coupling agent can improve the interfacial bonding strength and water resistance, and will not cause delamination to affect the final effect.

[0022] In this embodiment, the dispersant is one or several of the BYK-2000 series, the defoaming agent is one or several of the BYK-000 series, the leveling agent is one or several of the BYK-300 series; the mixed solvent is set as propylene glycol methyl ether acetate and xylene, the mixed solvent mixing ratio is 1:1; xylene is the main solvent used to adjust the viscosity of the coating during painting, to ensure that it can be fully leveled during painting; the BYK-2000 series is a high-molecular ultra-dispersant that can fully disperse graphene to avoid agglomeration, form a good two-dimensional network path, and also greatly reduce the viscosity of the grinding slurry.

[0023] In this embodiment, the zinc powder and mica powder are both selected as 800-mesh flaky structures, the graphene nanosheet is a multi-layer with a sheet diameter of 7 μm; the flexible epoxy resin is set as an epoxy equivalent of 700, and the breaking elongation is greater than 35%; the zinc powder and mica powder are both selected as flaky structures, which can synergize with graphene to improve the anti-corrosion function, i.e., the zinc powder can provide cathodic protection, and the mica powder can strengthen the labyrinth effect, i.e., the mica powder sheets will be arranged roughly parallel to the surface of the substrate under the action of surface tension and solvent evaporation, forming a layer upon a layer of shielding layer, so that the corrosion medium cannot directly reach the coating adhesion point.

[0024] In this embodiment, the curing agent is a modified amine curing agent, which is generally selected by direct purchase, and can be selected from polyamide, isophorone diamine, and mannich base modified amine, etc. Here, isophorone diamine is selected as the curing agent, which can well compatible with the material part flexibility, which is not described here.

[0025] In this embodiment, the main agent is composed of 20% flexible epoxy resin, 5% n-butyl glycidyl ether, 5% graphene nanosheet, 35% spherical alumina, 7% zinc powder, and 3% mica powder, and 1.5% γ-(2,3-epoxypropoxy) propyl trimethoxysilane; the additive is selected as 3% BYK-2152, 0.5% BYK-052, 0.3% BYK-306, and 1% fumed silica; the mixed solvent is selected as 18.7% propylene glycol methyl ether acetate and xylene mixed solution. The ceramic coating with the best balance and economy can be obtained.

[0026] The solvent-based graphene nanoceramic coating of this embodiment is made by the following steps:

[0027] S1. Filler treatment: spherical alumina, flaky zinc powder, and flaky mica powder are added to a mixer and mixed, during which γ-(2,3-epoxypropoxy) propyl trimethoxysilane diluted with propylene glycol methyl ether acetate is added, and after uniform low-speed stirring at 400 rpm, a filler mixture is formed, which is taken out and cooled for standby.

[0028] S2. Selecting graphite powder to prepare graphene sheets by liquid phase exfoliation method.

[0029] S3. Adding base material, i.e. flexible epoxy resin, active diluent and mixed solvent into a reaction kettle for stirring, then adding dispersing agent and other additives in sequence, and stirring at 2000 rpm for 40 minutes to obtain a basic slurry.

[0030] S4. Continuing to stir the basic slurry and adding filler mixture; after fully mixing, slowly and uniformly adding graphene sheet powder under medium speed stirring at 800 rpm, and finally stirring at 2200 rpm for 60 minutes to fully wet and disperse to obtain a coarse slurry.

[0031] S5. Grind the initial slurry in a basket sand mill to a fineness of less than or equal to 25 μm; which can effectively break the graphene agglomeration and uniformly distribute in the ceramic coating to form a continuous heat conduction network.

[0032] Obtain initial slurry

[0033] S6, Place the initial slurry in a reaction kettle, add fumed silica and part of the defoaming agent, fully stir at 600 rpm, adjust the viscosity, and filter with a 200 mesh filter to obtain the main agent, i.e. the main agent of the coating.

[0034] S7. Mix the main agent and the curing agent according to 4:1, and then airless spray.

[0035] The following are specific embodiments of the present application, which are used to specifically illustrate the present application. The preparation methods of the following examples are the same, and will not be listed one by one:

[0036] Example 1

[0037] 1. First, make the main agent (0.5 kg):

[0038] According to the mass percentage, take 20% of the flexible epoxy resin, 5% of the n-butyl glycidyl ether, 5% of the graphene nanosheet, 35% of the spherical alumina, 7% of the zinc powder, 3% of the mica powder, 1.5% of the γ-(2,3-epoxypropoxy) propyl trimethoxysilane, 3% of BYK-2152, 0.5% of BYK-052, 0.3% of BYK-306, 1% of fumed silica and 18.7% of mixed solvent, the mixed solvent is a mixed solution of propylene glycol methyl ether acetate and xylene mixed according to mass fraction 1:1; gradually mix to form the main agent at room temperature according to the preparation method;

[0039] 2. Mix the prepared main agent with the curing agent according to 4:1 to prepare the solvent type graphene nanoceramic coating finished product, wherein the curing agent is selected as isophorone diamine;

[0040] Test: The solvent type graphene nanoceramic coating product is sprayed by using airless spraying process, and then is shaped by heating curing. The heat flow meter method and salt spray test are used to measure the thermal conductivity and corrosion resistance. The measured indexes meet the use requirements, and the specific statistical table is shown.

[0041] Example 2

[0042] 1. First, make the main agent (0.5 kg):

[0043] According to the mass percentage, take 18% of the flexible epoxy resin, 3% of the n-butyl glycidyl ether, 4% of the graphene nanosheet, 30% of the spherical alumina, 8% of the zinc powder, 3% of the mica powder, 2% of the γ-(2,3-epoxypropoxy) propyl trimethoxysilane, 4.2% of BYK-2152, 0.6% of BYK-052, 0.7% of BYK-306, 1.5% of fumed silica and 25% of the mixed solvent, the mixed solvent is propylene glycol methyl ether acetate and xylene mixed according to the mass fraction 1:1 to form a mixed solution; according to the preparation method, gradually mix to form the main agent at room temperature;

[0044] 2. Mix the prepared main agent with the curing agent according to 4:1 to make the solvent type graphene nanoceramic coating product, wherein the curing agent is selected as isophorone diamine;

[0045] Test: The solvent type graphene nanoceramic coating product is sprayed by using airless spraying process, and then is shaped by heating curing. The heat flow meter method and salt spray test are used to measure the thermal conductivity and corrosion resistance. The measured indexes meet the use requirements, and the specific statistical table is shown.

[0046] Example 3

[0047] 1. First, make the main agent (0.5 kg):

[0048] According to the mass percentage, take 25% of the flexible epoxy resin, 4.2% of the n-butyl glycidyl ether, 6% of the graphene nanosheet, 40% of the spherical alumina, 6% of the zinc powder, 1% of the mica powder, 2% of the γ-(2,3-epoxypropoxy) propyl trimethoxysilane, 3% of BYK-2152, 0.5% of BYK-052, 0.3% of BYK-306, 1% of fumed silica and 11% of the mixed solvent, the mixed solvent is propylene glycol methyl ether acetate and xylene mixed according to the mass fraction 1:1 to form a mixed solution; according to the preparation method, gradually mix to form the main agent at room temperature;

[0049] 2. Mix the prepared main agent with the curing agent according to 4:1 to make the solvent type graphene nanoceramic coating product, wherein the curing agent is selected as isophorone diamine;

[0050] Test: The solvent type graphene nanoceramic coating product is sprayed by using airless spraying process, and then is shaped by heating curing. The heat flow meter method and salt spray test are used to measure the thermal conductivity and corrosion resistance. The measured indexes meet the use requirements, and the specific statistical table is shown.

[0051] Example 4

[0052] 1. First, make the main agent (0.5 kg):

[0053] According to the mass percentage, take 20% of the flexible epoxy resin, 5% of the isobutyl glycidyl ether, 4.5% of the graphene nanosheet, 35.5% of the spherical alumina, 7% of the zinc powder, 3% of the mica powder, 1.5% of the methyl triethoxysilane, 3% of BYK-2152, 0.5% of BYK-052, 0.3% of BYK-306, 1% of fumed silica, and 18.7% of the mixed solvent. The mixed solvent is a mixed solution of propylene glycol methyl ether acetate and xylene mixed in a mass ratio of 1:1; and the main agent is gradually mixed at room temperature according to the preparation method;

[0054] 2. Mix the prepared main agent with the curing agent according to 4:1 to make the solvent type graphene nanoceramic coating product, wherein the curing agent is selected as isophorone diamine;

[0055] Test: The solvent type graphene nanoceramic coating product is sprayed by using airless spraying process, and then is shaped by heating curing. The heat flow meter method and salt spray test are used to measure the thermal conductivity and corrosion resistance. The measured indexes meet the use requirements, and the specific statistical table is shown.

[0056] Example 5

[0057] 1. First, make the main agent (0.5 kg):

[0058] According to the mass percentage, take 20% of the flexible epoxy resin, 5% of the isobutyl glycidyl ether, 5.5% of the graphene nanosheet, 36.5% of the spherical alumina, 6% of the zinc powder, 3% of the mica powder, 1.5% of the methyl triethoxysilane, 3% of BYK-2152, 0.5% of BYK-052, 0.3% of BYK-306, 1% of fumed silica, and 17.7% of the mixed solvent. The mixed solvent is a mixed solution of propylene glycol methyl ether acetate and xylene mixed in a mass ratio of 1:1; and the main agent is gradually mixed at room temperature according to the preparation method;

[0059] 2. Mix the prepared main agent with the curing agent according to 4:1 to make the solvent type graphene nanoceramic coating product, wherein the curing agent is selected as isophorone diamine;

[0060] Test: The solvent type graphene nanoceramic coating product is sprayed by using airless spraying process and then shaped by heating curing. The heat flow meter method and salt spray test are used to determine the thermal conductivity and corrosion resistance. The measured indicators meet the use requirements, and the specific statistical table is shown.

[0061] Example 6

[0062] 1. First, make the main agent (0.5 kg):

[0063] According to the mass percentage, take 20% of the flexible epoxy resin, 5% of the tert-butyl glycidyl ether, 6% of the graphene nanosheet, 34% of the spherical alumina, 6% of the zinc powder, 4% of the mica powder, 1.5% of the phenyl trimethoxysilane, 3% of BYK-2152, 0.5% of BYK-052, 0.3% of BYK-306, 1% of fumed silica, and 18.7% of the mixed solvent. The mixed solvent is a mixed solution of propylene glycol methyl ether acetate and xylene mixed in a mass ratio of 1:1; gradually mix to form the main agent at room temperature according to the preparation method;

[0064] 2. Mix the prepared main agent with the curing agent according to 4:1 to make the solvent type graphene nanoceramic coating product, wherein the curing agent is selected as isophorone diamine;

[0065] Test: The solvent type graphene nanoceramic coating product is sprayed by using airless spraying process and then shaped by heating curing. The heat flow meter method and salt spray test are used to determine the thermal conductivity and corrosion resistance. The measured indicators meet the use requirements, and the specific statistical table is shown.

[0066] Example 7

[0067] 1. First, make the main agent (0.5 kg):

[0068] According to the mass percentage, take 20% of the flexible epoxy resin, 5% of the tert-butyl glycidyl ether, 6% of the graphene nanosheet, 34% of the spherical alumina, 6% of the zinc powder, 4% of the mica powder, 1.5% of the phenyl trimethoxysilane, 3% of BYK-2152, 0.5% of BYK-052, 0.3% of BYK-306, 1% of fumed silica, and 18.7% of the mixed solvent. The mixed solvent is a mixed solution of propylene glycol methyl ether acetate and xylene mixed in a mass ratio of 1:1; gradually mix to form the main agent at room temperature according to the preparation method;

[0069] 2. Mix the prepared main agent with the curing agent according to 4:1 to make the solvent type graphene nanoceramic coating product, wherein the curing agent is selected as isophorone diamine;

[0070] Test: The prepared solvent type graphene nanoceramic coating product is sprayed by using airless spraying process and is shaped by using heating curing method. The heat flow meter method and salt spray test are used to measure the heat conduction performance and corrosion resistance. The measured indexes meet the use requirements, and the specific statistical table is shown.

[0071] Finally, it should be pointed out that the above examples are only used to illustrate the technical solutions of the present application and are not limiting. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced by equivalents without departing from the purpose and scope of the present application, and they should be covered in the scope of the claims of the present application.

Claims

1. A solvent based graphene nanoceramic coating, characterized in that: The curing agent and the main agent are mixed in a ratio of 1:3-6; the main agent is composed of flexible epoxy resin, diluent, graphene nanosheet, spherical alumina, zinc powder, mica powder, silane coupling agent, fumed silica and additive.

2. The solvent-based graphene nanoceramic coating according to claim 1, characterized in that: The main agent is composed of 18-25% flexible epoxy resin, 3-7% diluent, 3-6% graphene nanosheet, 30-40% spherical alumina, 6-10% zinc powder, 1-5% mica powder, 1-2% silane coupling agent and the rest additive.

3. The solvent-based graphene nanoceramic coating according to claim 2, characterized in that: The rest additive is composed of 1-4% dispersant, 0.3-0.6% defoamer, 0.3-0.7% leveling agent, 0.5-1.5% fumed silica and 15-20% mixed solvent, and the percentage is the mass percentage of the main agent.

4. The solvent-based graphene nanoceramic coating of claim 2, wherein: The diluent is one or more of n-butyl glycidyl ether, isobutyl glycidyl ether and t-butyl glycidyl ether; the silane coupling agent is one or more of methyl triethoxysilane, methyl tetramethoxysilane, methyl tetraethoxysilane, phenyl trimethoxysilane, diphenyl dimethoxysilane, methyl phenyl dimethoxysilane and γ-(2,3-epoxypropoxy) propyl trimethoxysilane.

5. The solvent based graphene nanoceramic coating as claimed in claim 3, wherein: The dispersant is one or more of BYK-2000 series, the defoamer is one or more of BYK-000 series, the leveling agent is one or more of BYK-300 series, and the mixed solvent is a mixture of propylene glycol methyl ether acetate and dimethylbenzene in a mass ratio of 1:

1.

6. The solvent based graphene nanoceramic coating as claimed in claim 3, wherein: The zinc powder and mica powder are both selected in a sheet structure of 800 mesh, the graphene nanosheet is a multi-layer structure with a sheet diameter of 6-8 μm, and the flexible epoxy resin has an epoxy equivalent weight of 550-800 and an elongation at break of more than 30%.

7. The solvent based graphene nanoceramic coating as claimed in claim 1, wherein: The curing agent is a modified amine curing agent.

8. The solvent based graphene nanoceramic coating as claimed in claim 1, wherein: The main agent is composed of 20% flexible epoxy resin, 5% n-butyl glycidyl ether, 5% graphene nanosheet, 35% spherical alumina, 7% zinc powder, 3% mica powder and 1.5% γ-(2,3-epoxypropoxy) propyl trimethoxysilane; the additive is selected as 3% BYK-2152, 0.5% BYK-052, 0.3% BYK-306, 1% fumed silica and 18.7% mixed solvent. The mixed solvent is a mixture of propylene glycol methyl ether acetate and dimethylbenzene in a mass ratio of 1:1.

Images