Marine heavy anti-corrosion coating and preparation method thereof

Abstract

The invention provides an offshore heavy anti-corrosion coating and a preparation method thereof. The offshore heavy anti-corrosion coating comprises the following raw materials in parts by weight: 40-70 parts of a resin polymer; 20-35 parts of a curing agent; 10 to 25 parts of pigment; 0.5 to 2 parts of modified nano particles; 0.03 to 3 parts of an auxiliary agent; 0.001 to 1 part of a drier; the modified nano particles are obtained by modifying a two-dimensional nano material through phosphorus-doped carbon dots. The phosphorus-doped carbon dots are used for modifying the two-dimensional flaky nano-material, the dispersity and compatibility of the modified nano-particles in the heavy anti-corrosion coating are improved, the phosphorus-doped carbon dots are added, a P-O-Fe protective layer can be formed on the surface of a metal matrix, an additional passivation function is provided, and continuous corrosion of the metal matrix is greatly avoided; the two-dimensional nano material is added, so that the erosion path of corrosive ions is prolonged, and the interaction between the heavy anti-corrosion coating and the surface of a matrix is also enhanced; the marine heavy anti-corrosion coating disclosed by the invention has good adhesive force, corrosion resistance and salt spray resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of anti-corrosion coatings, and in particular to a marine heavy-duty anti-corrosion coating and a preparation method thereof. Background Art

[0002] As a renewable and renewable energy source, wind energy offers advantages such as large reserves, wide distribution, and low carbon footprint. It holds significant potential for promoting energy transition and building a new energy system dominated by renewable energy. However, due to the complex offshore environment, wind turbines are exposed to high temperatures, high humidity, and high salinity, resulting in high corrosion activity and a high risk of corrosion. To extend the life of wind turbines, reduce maintenance costs, and mitigate safety incidents, it is crucial to develop an anti-corrosion coating suitable for use in marine atmospheric environments.

[0003] Currently, the most effective strategy for preventing metal corrosion is to cover the surface with a coating to prevent contact between the corrosive medium and the metal surface. Waterborne epoxy resin is a typical organic polymer coating with advantages such as low volatile content, strong adhesion, and good chemical stability. It is widely used in offshore facilities, bridges, buildings, and other fields. However, the shielding ability of a single waterborne epoxy resin against corrosive ions is limited, and the volatilization of the solvent during the curing process can produce micropores and cracks, which cannot provide long-term protection for the substrate. Therefore, improving the shielding performance of the coating material against corrosive media is crucial to extending the service life of metal materials. Summary of the Invention

[0004] The technical problem to be solved by the present invention is how to enable the coating to provide long-term protection to the metal substrate.

[0005] The present invention solves the above technical problems through the following technical means:

[0006] A first aspect of the present invention provides a marine heavy-duty anti-corrosion coating comprising the following raw materials in parts by weight:

[0007]

[0008] The modified nanoparticles are obtained by modifying two-dimensional nanomaterials through phosphorus-doped carbon dots.

[0009] Beneficial effects: The present invention improves the dispersibility and compatibility of modified nanoparticles in heavy-duty anti-corrosion coatings by modifying two-dimensional flaky nanomaterials through phosphorus-doped carbon dots. The addition of phosphorus-doped carbon dots can form a PO-Fe protective layer on the surface of the metal substrate, providing additional passivation function, which greatly avoids the continuous corrosion of the metal substrate; the addition of two-dimensional nanomaterials prolongs the erosion path of corrosive ions and enhances the interaction between the heavy-duty anti-corrosion coating and the substrate surface; the marine heavy-duty anti-corrosion coating of the present invention has good adhesion, corrosion resistance and salt spray resistance.

[0010] Preferably, the two-dimensional nanomaterial is one or more of zirconium phosphate or boron nitride.

[0011] Preferably, the phosphorus-doped carbon dots are prepared by mixing glucose and phosphoric acid in a mass ratio of 0.5-1:5 by a hydrothermal method.

[0012] Preferably, the resin polymer is one or more of epoxy resin, polyurethane resin, acrylic resin or fluorocarbon resin.

[0013] Preferably, the curing agent is one or more of a polyamide epoxy curing agent or a modified amine epoxy curing agent.

[0014] Preferably, the pigment is one or more of rutile titanium dioxide, talc or ceramic powder.

[0015] Preferably, the auxiliary agent is one or more of a leveling agent, a defoaming agent, a wetting agent or an anti-settling agent.

[0016] Preferably, the leveling agent is one or more of silicone oil and polysiloxane.

[0017] Preferably, the defoaming agent is one or more of polyamide, polyphosphate or mineral oil.

[0018] Preferably, the wetting agent is one or more of polyether-modified silicone oil and surfactant.

[0019] Preferably, the anti-settling agent is one or more of fumed silica and organic bentonite.

[0020] Preferably, the drying agent is one or more of dibutyltin dilaurate or 2,4,6-tris(dimethylaminomethyl)phenol.

[0021] A second aspect of the present invention provides a method for preparing the above-mentioned marine heavy-duty anti-corrosion coating, comprising the following steps:

[0022] S1: dissolving the curing agent in water and stirring evenly to obtain a curing solution;

[0023] S2: mixing the additive with water, then adding the resin polymer and the modified nanoparticles and crushing them, and then adding the pigment and the drying agent and crushing them to obtain the coating;

[0024] S3 mixes the solidified solution with the coating to obtain a marine heavy-duty anti-corrosion coating.

[0025] Preferably, the modified nanoparticles are prepared according to the following method:

[0026] Glucose and phosphoric acid are mixed and heated using a hydrothermal method, then purified by dialysis and freeze-dried to obtain phosphorus-doped carbon dots; the two-dimensional nanomaterial is exfoliated using a mechanical ultrasonic method, and the exfoliated two-dimensional nanomaterial is mixed and modified with phosphorus-doped carbon dots to obtain modified nanoparticles.

[0027] Preferably, the heating temperature is 120° C. and the heating time is 4 hours. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 This is an optical appearance image of the heavy-duty anti-corrosion coating of Example 1 after 400 hours of neutral salt spray test;

[0029] Figure 2 This is an optical appearance image of the heavy-duty anti-corrosion coating of Comparative Example 1 after 400h neutral salt spray test;

[0030] Figure 3 This is the optical appearance of the heavy-duty anti-corrosion coating of Comparative Example 2 after 400h neutral salt spray test. DETAILED DESCRIPTION

[0031] To make the objectives, technical solutions, and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts shall fall within the scope of protection of the present invention.

[0032] Unless otherwise specified, the test materials and reagents used in the following examples can be obtained from commercial sources.

[0033] If no specific techniques or conditions are specified in the examples, they can be carried out according to the techniques or conditions described in the literature in the field or according to the product instructions.

[0034] Example 1

[0035] This embodiment provides a marine heavy-duty anti-corrosion coating and a preparation method thereof, as follows:

[0036] The marine heavy-duty anti-corrosion coating comprises the following raw materials in parts by weight:

[0037]

[0038] The modified zirconium phosphate is obtained by modifying zirconium phosphate with phosphorus-doped carbon dots.

[0039] The preparation method of the marine heavy-duty anti-corrosion coating specifically comprises the following steps:

[0040] Preparation of S1 modified zirconium phosphate:

[0041] Glucose and phosphoric acid were mixed in a 0.5:5 mass ratio in a polytetrafluoroethylene-lined stainless steel autoclave and reacted at 120°C for 4 hours. The mixture was then purified by dialysis and freeze-dried to produce phosphorus-doped carbon dots. The zirconium phosphate was then subjected to mechanical ultrasonic exfoliation, which disrupted interlayer forces (such as van der Waals forces and hydrogen bonds) within the zirconium phosphate, exposing more active sites within the monolayer nanosheets. The exfoliated zirconium phosphate was then mixed with phosphorus-doped carbon dots in a 10:1 mass ratio to produce the modified zirconium phosphate.

[0042] Preparation of S2 offshore heavy-duty anti-corrosion coating:

[0043] A polyamide epoxy curing agent is dissolved in deionized water and stirred evenly to obtain a curing solution; fumed silica, polyether modified silicone oil and deionized water are mixed, epoxy resin (DY-50), modified zirconium phosphate and polyamide are added and ultrasonically crushed for 1 hour, and then silicone oil, rutile titanium dioxide and dibutyltin dilaurate are added and ultrasonically crushed for 0.5 hour to obtain a coating; the curing solution and the coating are mixed evenly to obtain a marine heavy-duty anti-corrosion coating.

[0044] Example 2

[0045] This embodiment provides a marine heavy-duty anti-corrosion coating and a preparation method thereof, as follows:

[0046] The marine heavy-duty anti-corrosion coating comprises the following raw materials in parts by weight:

[0047]

[0048] The modified zirconium phosphate is obtained by modifying zirconium phosphate with phosphorus-doped carbon dots.

[0049] The preparation method of the marine heavy-duty anti-corrosion coating specifically comprises the following steps:

[0050] Preparation of S1 modified zirconium phosphate:

[0051] Glucose and phosphoric acid were mixed in a 1:5 mass ratio in a polytetrafluoroethylene-lined stainless steel autoclave and reacted at 120°C for 4 hours. The mixture was then purified by dialysis and freeze-dried to produce phosphorus-doped carbon dots. The zirconium phosphate was then subjected to mechanical ultrasonic exfoliation, which disrupted interlayer forces (such as van der Waals forces and hydrogen bonds) within the zirconium phosphate, exposing more active sites within the monolayer nanosheets. The exfoliated zirconium phosphate was then mixed with phosphorus-doped carbon dots in an 8:1 mass ratio to produce the modified zirconium phosphate.

[0052] Preparation of S2 offshore heavy-duty anti-corrosion coating:

[0053] A polyamide epoxy curing agent is dissolved in deionized water and stirred evenly to obtain a curing solution; fumed silica, polyether modified silicone oil and deionized water are mixed, polyurethane resin (R8300), modified zirconium phosphate and polyamide are added and ground for 2 hours, and then silicone oil, talc powder and dibutyltin dilaurate are added and ground for 1 hour to obtain a coating; the curing solution and the coating are mixed evenly to obtain a marine heavy-duty anti-corrosion coating.

[0054] Example 3

[0055] This embodiment provides a marine heavy-duty anti-corrosion coating and a preparation method thereof, as follows:

[0056] The marine heavy-duty anti-corrosion coating comprises the following raw materials in parts by weight:

[0057]

[0058] The modified zirconium phosphate is obtained by modifying zirconium phosphate with phosphorus-doped carbon dots.

[0059] The preparation method of the marine heavy-duty anti-corrosion coating specifically comprises the following steps:

[0060] Preparation of S1 modified zirconium phosphate:

[0061] Glucose and phosphoric acid were mixed in a 1:5 mass ratio in a polytetrafluoroethylene-lined stainless steel autoclave and reacted at 120°C for 4 hours. The mixture was then purified by dialysis and freeze-dried to produce phosphorus-doped carbon dots. The zirconium phosphate was then subjected to mechanical ultrasonic exfoliation, which disrupted interlayer forces (such as van der Waals forces and hydrogen bonds) within the zirconium phosphate, exposing more active sites within the monolayer nanosheets. The exfoliated zirconium phosphate was then mixed with phosphorus-doped carbon dots in a 5:1 mass ratio to produce the modified zirconium phosphate.

[0062] Preparation of S2 offshore heavy-duty anti-corrosion coating:

[0063] A polyamide epoxy curing agent is dissolved in deionized water and stirred evenly to obtain a curing solution; fumed silica, polyether modified silicone oil and deionized water are mixed, acrylic resin (SE-2194), modified zirconium phosphate and polyamide are added and ultrasonically crushed for 1 hour, and then silicone oil, ceramic powder and dibutyltin dilaurate are added and ground for 1 hour to obtain a coating; the curing solution and the coating are mixed evenly to obtain a marine heavy-duty anti-corrosion coating.

[0064] Example 4

[0065] This embodiment provides a marine heavy-duty anti-corrosion coating and a preparation method thereof, as follows:

[0066] The marine heavy-duty anti-corrosion coating comprises the following raw materials in parts by weight:

[0067]

[0068]

[0069] The surfactant is sodium dodecylbenzenesulfonate;

[0070] The modified zirconium phosphate is obtained by modifying zirconium phosphate with phosphorus-doped carbon dots.

[0071] The preparation method of the marine heavy-duty anti-corrosion coating specifically comprises the following steps:

[0072] Preparation of S1 modified zirconium phosphate:

[0073] Glucose and phosphoric acid were mixed in a 0.75:5 mass ratio and introduced into a polytetrafluoroethylene-lined stainless steel autoclave. The mixture was reacted at 120°C for 4 hours. The mixture was then purified by dialysis and freeze-dried to produce phosphorus-doped carbon dots. The zirconium phosphate was then subjected to mechanical ultrasonic exfoliation. This destroyed the interlayer forces (such as van der Waals forces and hydrogen bonds) within the zirconium phosphate, exposing more active sites in the monolayer nanosheets. The exfoliated zirconium phosphate was then mixed with phosphorus-doped carbon dots in a 5:1 mass ratio to produce the modified zirconium phosphate.

[0074] Preparation of S2 offshore heavy-duty anti-corrosion coating:

[0075] The modified amine epoxy curing agent is dissolved in deionized water and stirred evenly to obtain a curing solution; fumed silica, polyether modified silicone oil and deionized water are mixed, fluorocarbon resin (GK-570), modified zirconium phosphate and polyamide are added and ground for 2 hours, and then silicone oil, talc powder and dibutyltin dilaurate are added and ultrasonically crushed for 0.5 hours to obtain a coating; the curing solution and the coating are mixed evenly to obtain a marine heavy-duty anti-corrosion coating.

[0076] Example 5

[0077] This embodiment provides a marine heavy-duty anti-corrosion coating and a preparation method thereof. The difference between this embodiment and Example 1 is that the modified nanoparticles are different. This embodiment uses modified boron nitride. The rest is the same as Example 1.

[0078] Comparative Example 1

[0079] This comparative example provides a marine heavy-duty anti-corrosion coating and a preparation method thereof. This comparative example differs from Example 1 in that the nanoparticles are not modified by phosphorus-doped carbon dots, and zirconium phosphate is used directly.

[0080] Comparative Example 2

[0081] This comparative example provides a marine heavy-duty anti-corrosion coating and a preparation method thereof. This comparative example differs from Example 1 in that no modified nanoparticles are added.

[0082] Experimental example

[0083] The marine heavy anti-corrosion coatings of Examples 1-5 and Comparative Examples 1-2 were applied to the surface of a Q235 test piece to test the performance of the coating. The Q235 test piece was pretreated and polished with sandpaper until the surface was smooth and bright. The polished Q235 test piece was placed in an acetone solution and ultrasonicated for 30 minutes, and then dried at room temperature for use.

[0084] The test performance is as follows: adhesion test according to GB / T 9286-2021, pencil hardness test according to GB / T6739-2006, 30d electrochemical impedance spectroscopy according to ISO 16773-4:2009, 240h acid, alkali and salt resistance test according to GB / T9274-1988, and 400h neutral salt spray resistance test according to GB / T 1771-2007. The test results are shown in Table 1.

[0085] Table 1

[0086]

[0087] According to the data in Table 1, the marine heavy-duty anti-corrosion coating of this embodiment has good adhesion, hardness and corrosion resistance. This embodiment improves the dispersibility and compatibility of two-dimensional nanomaterials in the heavy-duty anti-corrosion coating by using phosphorus-doped carbon dots prepared by a hydrothermal method to achieve long-term corrosion protection of the metal substrate. The mechanical properties and acid, alkali and salt resistance of the marine heavy-duty anti-corrosion coating with the addition of modified nanoparticles are greatly improved.

[0088] Furthermore, the addition of phosphorus-doped carbon dots provides an additional passivation function by forming a PO-Fe protective layer on the metal substrate surface, significantly preventing continued corrosion at the metal interface. This invention provides a new approach to the selection and design of functional fillers in heavy-duty anti-corrosion coatings for harsh environments, promoting the development of marine metal corrosion protection.

[0089] according to Figure 1-Figure 3 As shown, the marine heavy-duty anti-corrosion coating of Example 1 maintains good corrosion resistance in the neutral salt spray resistance test, while the marine heavy-duty anti-corrosion coatings of Comparative Examples 1 and 2 are severely corroded in the neutral salt spray resistance test, indicating that the marine heavy-duty anti-corrosion coatings of Comparative Examples 1 and 2 have poor corrosion resistance.

[0090] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A marine heavy-duty anti-corrosion coating, characterized in that: The following raw materials are included in parts by weight: The modified nanoparticles are obtained by modifying two-dimensional nanomaterials through phosphorus-doped carbon dots.

2. The marine heavy-duty anti-corrosion coating according to claim 1, characterized in that: The two-dimensional nanomaterial is one or more of zirconium phosphate and boron nitride.

3. The marine heavy-duty anti-corrosion coating according to claim 1 or 2, characterized in that: The phosphorus-doped carbon dots are prepared by mixing glucose and phosphoric acid in a mass ratio of 0.5-1:5 through a hydrothermal method.

4. The marine heavy-duty anti-corrosion coating according to claim 2, characterized in that: The mass ratio of the phosphorus-doped carbon dots to the two-dimensional nanomaterials is 1:5-10.

5. The marine heavy-duty anti-corrosion coating according to claim 1, characterized in that: The resin polymer is one or more of epoxy resin, polyurethane resin, acrylic resin or fluorocarbon resin; the curing agent is one or more of DY-175 or modified amine epoxy curing agent; and the pigment is one or more of rutile titanium dioxide, talc or ceramic powder.

6. The marine heavy-duty anti-corrosion coating according to claim 1, characterized in that: The auxiliary agent is one or more of a leveling agent, a defoaming agent, a wetting agent or an anti-settling agent.

7. The marine heavy-duty anti-corrosion coating according to claim 6, characterized in that: The leveling agent is one or more of silicone oil or polysiloxane, the defoaming agent is one or more of polyamide, polyphosphate or mineral oil, the wetting agent is one or more of polyether-modified silicone oil or surfactant, and the anti-settling agent is one or more of fumed silica or organic bentonite.

8. The marine heavy-duty anti-corrosion coating according to claim 1, characterized in that: The drying agent is one or more of dibutyltin dilaurate and 2,4,6-tris(dimethylaminomethyl)phenol.

9. The method for preparing a marine heavy-duty anti-corrosion coating according to any one of claims 1 to 8, characterized in that: The following steps are involved: S1: dissolving the curing agent in water and stirring evenly to obtain a curing solution; S2: mixing the additive with water, then adding the resin polymer and the modified nanoparticles and crushing them, and then adding the pigment and the drying agent and crushing them to obtain the coating; S3 mixes the solidified solution with the coating to obtain a marine heavy-duty anti-corrosion coating.

10. The method for preparing a marine heavy-duty anti-corrosion coating according to claim 9, characterized in that: The modified nanoparticles are prepared according to the following method: Glucose and phosphoric acid are mixed and heated by a hydrothermal method, then purified by dialysis and freeze-dried to obtain phosphorus-doped carbon dots; the two-dimensional nanomaterial is exfoliated by a mechanical ultrasonic method, and the exfoliated two-dimensional nanomaterial is mixed and modified with the phosphorus-doped carbon dots to obtain modified nanoparticles; the heating temperature is 120°C and the heating time is 4 hours.

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