A metal-based self-polishing antifouling composite material, coating and method for preparing the same

Abstract

The present application belongs to the technical field of coating materials, and particularly relates to a metal-based self-polishing antifouling composite material, a coating and a preparation method thereof. The present application provides a metal-based self-polishing antifouling composite material, which comprises the following components in mass fraction: 0.5-20% of a metal bacteriostatic agent, 0.5-40% of a water-soluble metal salt, and the balance of a metal alloy powder. The present application realizes the dual effects of antifouling factor slow release and self-polishing effect through the compounding of the metal alloy powder, the metal bacteriostatic agent and the water-soluble metal salt. On the one hand, the metal bacteriostatic agent (such as Cu, Zn and Ag) in the coating is slowly released in the corrosion process to inhibit the adhesion of microorganisms; on the other hand, the water-soluble metal salt gradually dissolves in the seawater environment to form a porous structure, which is synergistic with the corrosion of the metal alloy to promote the peeling of the outer layer material, expose the fresh surface and continuously maintain the antifouling activity.

Description

Technical Field

[0001] This invention belongs to the field of coating materials technology, specifically relating to a metal-based self-polishing and anti-fouling composite material, coating, and preparation method thereof. Background Technology

[0002] In marine environments, the attachment of fouling organisms (such as barnacles and algae) increases frictional resistance, energy consumption, and accelerates material corrosion in equipment such as ships and platforms. Traditional antifouling coatings rely on the release of toxic substances (such as organotin), posing environmental pollution problems. Other common protective coatings mainly include metallic coatings, ceramic coatings, and organic coatings. Different types of protective coatings still have their own problems: for example, stainless steel coatings have good corrosion resistance but lack antifouling properties; the antifouling performance of ceramic coatings is also a weakness; organic coatings have relatively low hardness, resulting in poor cavitation resistance, and also suffer from short antifouling life, weak adhesion, and easy peeling. In addition, although current self-polishing coatings can achieve surface renewal through hydrolysis, they still have a limited antifouling life. Therefore, developing a metallic coating material with long-lasting antifouling activity is of great significance. Summary of the Invention

[0003] In view of this, the purpose of this invention is to provide a metal-based self-polishing antifouling composite material, a coating, and a method for preparing the same. The coating prepared using the metal-based self-polishing antifouling composite material of this invention exhibits durable antifouling activity and good antibacterial properties.

[0004] This invention provides a metal-based self-polishing and anti-fouling composite material, comprising the following components by mass fraction:

[0005] The metal antibacterial agent is 0.5-20%, the water-soluble metal salt is 0.5-40%, and the balance is metal alloy powder.

[0006] Preferably, the metal antibacterial agent includes one or more of copper, zinc, and silver.

[0007] Preferably, the water-soluble metal salt includes one or more of barium salts, calcium salts, cobalt salts, potassium salts, scandium salts, lithium salts, magnesium salts, sodium salts, nickel salts, rubidium salts, strontium salts, copper salts, and yttrium salts.

[0008] Preferably, the water-soluble metal salt includes one or more of barium acetate, barium bromide, barium chlorate, barium chloride, barium iodide, calcium chloride, calcium bromide, cobalt bromide, cobalt chloride, potassium chloride, scandium sulfate, lithium molybdate, magnesium chloride, magnesium bromide, sodium chloride, nickel chloride, nickel bromide, nickel iodide, rubidium bromide, strontium chloride, copper chloride, and yttrium chloride.

[0009] Preferably, the metal alloy powder is a powder prepared from a metal alloy material, which includes one or more of stainless steel, copper alloy, titanium alloy, aluminum alloy, high-temperature alloy, high-entropy alloy, and amorphous alloy.

[0010] Preferably, the metal antibacterial agent is 1-4% of the mass of the metal alloy powder; the mass ratio of the sum of the metal alloy powder and the metal antibacterial agent to the mass of the water-soluble metal salt is 60-95:5-40.

[0011] This invention also provides a method for preparing the metal-based self-polishing and anti-fouling composite material described in the above technical solution, comprising the following steps:

[0012] The metal-based self-polishing and anti-fouling composite material is obtained by mixing a metal antibacterial agent, a water-soluble metal salt, and a metal alloy powder.

[0013] The present invention also provides a metal-based self-polishing anti-fouling coating, wherein the material of the coating is the metal-based self-polishing anti-fouling composite material described in the above technical solution or the metal-based self-polishing anti-fouling composite material obtained by the above preparation method.

[0014] The present invention also provides a method for preparing the metal-based self-polishing and anti-fouling coating described in the above technical solution, comprising the following steps:

[0015] Laser additive manufacturing of composite materials is performed on the substrate surface to form a metal-based self-polishing and anti-fouling coating on the substrate surface;

[0016] The composite material is the metal-based self-polishing and anti-fouling composite material described in the above technical solution or the metal-based self-polishing and anti-fouling composite material obtained by the above preparation method.

[0017] Preferably, the conditions for laser additive manufacturing include: power 400~8000W, scanning speed 5~1000mm / s, and powder feed rate 2~30g / min.

[0018] Compared with the prior art, the present invention has the following beneficial effects:

[0019] This invention provides a metal-based self-polishing and anti-fouling composite material, comprising the following components by mass fraction: 0.5-20% metal antibacterial agent, 0.5-40% water-soluble metal salt, and the balance being metal alloy powder.

[0020] This invention achieves a dual effect of slow-release of antifouling agents and self-polishing by combining metal alloy powder, metal antibacterial agents, and water-soluble metal salts. On one hand, the metal antibacterial agents (such as Cu, Zn, and Ag) in the coating are slowly released during corrosion, inhibiting microbial adhesion. On the other hand, the water-soluble metal salts gradually dissolve in the seawater environment to form a porous structure, which, in synergy with the corrosion of the metal alloy, promotes the peeling off of the outer layer material, exposing a fresh surface and maintaining antifouling activity. After the formation of the porous structure, metal ions are released from the corrosion interface, further synergistically killing bacteria and inhibiting microbial metabolism. The data from the examples demonstrate that the coating made using the metal-based self-polishing antifouling composite material of this invention has long-lasting antifouling activity and good antibacterial properties.

[0021] Existing laser additive manufacturing technologies are mostly used for forming single metals or alloys, lacking the design of multifunctional composite materials specifically for marine antifouling needs. This invention provides a method for preparing a metal-based self-polishing antifouling coating. Leveraging the flexibility of laser additive manufacturing processes, a gradient distribution of water-soluble metal salt layers can be achieved, optimizing the balance between antifouling performance and mechanical strength, and enabling controllable coating material structure. The coating obtained by this invention exhibits high bonding strength between itself and the protected substrate. Attached Figure Description

[0022] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0023] Figure 1 This is a flowchart illustrating the preparation process of the metal-based self-polishing anti-fouling coating in the embodiments;

[0024] Figure 2 The graphs show the release of Cu ions from the coatings of Example 1 and Comparative Example 1 over 120 consecutive days. Detailed Implementation

[0025] This invention provides a metal-based self-polishing and anti-fouling composite material, comprising the following components by mass fraction:

[0026] The metal antibacterial agent is 0.5-20%, the water-soluble metal salt is 0.5-40%, and the balance is metal alloy powder.

[0027] Unless otherwise specified, all materials and equipment used in this invention are commercially available products in the field.

[0028] In this invention, the metal antibacterial agent preferably includes one or more of copper, zinc, and silver, and can be an element or an alloy; the metal antibacterial agent provides an antifouling element and is a bactericidal component in a metal-based self-polishing antifouling composite material. The metal antibacterial agent is preferably a nano or micron powder.

[0029] In this invention, the mass fraction of the metal antibacterial agent in the metal-based self-polishing antifouling composite material is preferably 2-15%, specifically 0.5%, 1.35%, 2%, 2.85%, 5%, 10%, 12%, 13.6%, 15%, 15.2%, 16.8%, 18.4%, or 20%.

[0030] In this invention, the metal antibacterial agent is preferably 1 to 4% of the mass of the metal alloy powder, specifically 1.5%, 2% or 3%.

[0031] In this invention, the water-soluble metal salt preferably includes one or more of barium salts, calcium salts, cobalt salts, potassium salts, scandium salts, lithium salts, magnesium salts, sodium salts, nickel salts, rubidium salts, strontium salts, copper salts, and yttrium salts. More preferably, it includes one or more of barium acetate, barium bromide, barium chlorate, barium chloride, barium iodide, calcium chloride, calcium bromide, cobalt bromide, cobalt chloride, potassium chloride, scandium sulfate, lithium molybdate, magnesium chloride, magnesium bromide (MgBr2), sodium chloride, nickel bromide, nickel fluoride, nickel iodide, rubidium bromide, strontium chloride (SrCl2), copper chloride (CuCl2), and yttrium chloride. The water-soluble metal salt is preferably a nano or micron powder.

[0032] In this invention, the mass ratio of the sum of the metal alloy powder and the metal antibacterial agent to the water-soluble metal salt is preferably 60~95:5~40, specifically 92:8, 84:16, 76:24, 68:32, 60:40, 90:10 or 95:5.

[0033] In this invention, the metal alloy powder is preferably a powder prepared from metal alloy materials. The metal alloy materials preferably include one or more of stainless steel, copper alloys, titanium alloys, aluminum alloys, high-temperature alloys, high-entropy alloys, and amorphous alloys. The stainless steel includes 316L stainless steel, 904L stainless steel, or 2205 duplex stainless steel; the copper alloy includes Cu5Sn; the titanium alloy includes Ti6Al4V; the aluminum alloy includes AlSi alloy; the high-temperature alloy includes Inconel 625 or Stellite 6; the high-entropy alloy includes CoCrNi or AlCoCrFeNi; and the amorphous alloy includes FeCrMoCBY. In specific embodiments, NiCrCo-based medium-entropy alloys, 316L stainless steel, Ti-6Al-4V, or AlSi10Mg are used. The metal alloy powder is preferably prepared by ball milling or gas atomization.

[0034] This invention provides a method for preparing the metal-based self-polishing and anti-fouling composite material described in the above technical solution, comprising the following steps:

[0035] The metal-based self-polishing antifouling coating composite material is obtained by mixing a metal antibacterial agent, a water-soluble metal salt, and a metal alloy powder.

[0036] In this invention, the mixing is preferably mechanical mixing or spray granulation.

[0037] This invention provides a metal-based self-polishing anti-fouling coating, wherein the coating material is the metal-based self-polishing anti-fouling composite material described in the above technical solution or the metal-based self-polishing anti-fouling composite material obtained by the above preparation method.

[0038] In this invention, the coating is preferably a gradient structure, which can be: the content of metal antibacterial agent decreases sequentially from the protected substrate to the coating surface, and / or the content of water-soluble metal salt increases sequentially.

[0039] In this invention, the thickness of the coating is preferably 500~2000μm.

[0040] This invention provides a method for preparing the metal-based self-polishing and anti-fouling coating described in the above technical solution, comprising the following steps:

[0041] Laser additive manufacturing of composite materials is used on the substrate surface to form a metal-based self-polishing and anti-fouling coating on the substrate surface;

[0042] The composite material is the metal-based self-polishing and anti-fouling composite material described in the above technical solution or the metal-based self-polishing and anti-fouling composite material obtained by the above preparation method.

[0043] In this invention, the substrate is preferably a metal alloy substrate, and the metal alloy substrate preferably includes a 304 stainless steel substrate.

[0044] In this invention, the laser additive manufacturing preferably includes powder-feed laser additive manufacturing, and the conditions for the laser additive manufacturing preferably include: power 400~2000W, scanning speed 5~200mm / s, and powder feeding rate 4~30g / min; specifically, it can be: power 500W, scanning speed 10mm / s, and powder feeding rate 8g / min; or laser power 800W, scanning speed 10mm / s, and powder feeding rate 8g / min; or power 800W, scanning speed 10mm / s, and powder feeding rate 12g / min; or power 800W, scanning speed 15mm / s, and powder feeding rate 2.4g / min; or power 150W, and scanning speed 1000mm / s.

[0045] In this invention, the laser additive manufacturing can be performed sequentially using composite materials with different contents of water-soluble metal salts to form a gradient coating.

[0046] This invention achieves long-lasting antifouling through the controlled dissolution of water-soluble metal salts in seawater and a surface self-renewal process (self-polishing). The coating releases bactericidal components in seawater, with the release rate decreasing as the coating remains in the seawater (the surface area of ​​the fresh alloy in contact with seawater decreases, and some areas are blocked by oxides, making it difficult for the bactericidal components to be released). When seawater comes into contact with the soluble metal salts, the salts dissolve, forming pores and exposing more of the metal alloy surface, allowing for supplemental release of the bactericidal components. As the material remains in seawater for an extended period, the porous surface of the metal alloy experiences corrosion, leading to a decrease in bonding strength. Under the shear forces of seawater erosion, the surface layer gradually peels off, achieving continuous surface renewal.

[0047] To further illustrate the present invention, the metal-based self-polishing anti-fouling composite material, coating and preparation method of the present invention are described in detail below with reference to the accompanying drawings and embodiments, but these should not be construed as limiting the scope of protection of the present invention.

[0048] Example 1

[0049] A metal-based self-polishing and anti-fouling composite material was prepared by mechanical mixing, comprising the following components:

[0050] NiCrCo medium-entropy alloy powder, its composition is Co: 34.14 wt.%, Cr: 30.14 wt.%, Ni: balance).

[0051] The mass fraction of copper (Cu) is 0.5% to 10%, specifically set at 0.5%, 5%, or 10%.

[0052] The mass fraction of the water-soluble metal salt potassium chloride is 5%.

[0053] Powder mixing process: Using steel balls with a diameter of 12 mm, the ball-to-material ratio is 1:2. The mixture is ball-milled at 200 rpm for 6 hours, and then ball-milled at 250 rpm for 3 hours to obtain mixed powder.

[0054] A copper-containing NiCrCo medium-entropy alloy coating with a thickness of 500 μm was prepared on the surface of a 304 stainless steel substrate using a laser additive manufacturing process with mixed powders. The laser additive manufacturing process was as follows: power 500W, scanning speed 10mm / s, powder feed rate 8g / min.

[0055] Test Example 1

[0056] The bonding strength was tested according to GB / T 44990-2024;

[0057] The antibacterial performance was tested using the plate count method. The specific test method is as follows: The samples were classified and placed in 24-well plates. An appropriate amount of Pseudomonas aeruginosa bacterial suspension was added to the sample surface according to the specific surface area and co-cultured for 24 hours. After that, the samples were diluted, plated, and incubated for another 48 hours. Plate counts were performed and the antibacterial rate relative to the 316L stainless steel coating (control group) was calculated.

[0058] The cumulative dissolution concentration of metal ions (antibacterial ion concentration) was determined by inductively coupled plasma mass spectrometry (ICP-MS).

[0059] Example 1 shows that the antibacterial performance test results of the coating indicate that the copper-containing NiCrCo medium-entropy alloy coating has a significant inhibitory effect on Pseudomonas aeruginosa, a typical corrosive marine bacterium. The antibacterial rate of the coating, the cumulative release concentration of Cu ions, and the bonding strength between the coating and the substrate are as follows:

[0060] When the copper content is 10%, the antibacterial rate can reach 99.1%; the cumulative release concentration of Cu ions on day 120 is 46 μg / L; and the bonding strength between the coating and the substrate is 692 MPa.

[0061] When the copper content is 5%, the antibacterial rate is 97.9%; the cumulative release concentration of Cu ions on day 120 is 32 μg / L; and the bonding strength between the coating and the substrate is 673 MPa.

[0062] When the copper content is 0.5%, the antibacterial rate is 96.3%; the cumulative release concentration of Cu ions on day 120 is 18 μg / L; and the bonding strength between the coating and the substrate is 653 MPa.

[0063] Figure 2 The graph shows the release of Cu ions from the coating of Example 1 over 120 consecutive days. It can be seen that the coating of Example 1 can release Cu ions persistently.

[0064] Example 2

[0065] A series of copper-containing NiCrCo medium-entropy alloy powders were prepared by mechanical mixing (the composition of the NiCrCo medium-entropy alloy was the same as in Example 1). The mass fraction of Cu in the copper-containing NiCrCo medium-entropy alloy powders was set to 5%, 10%, 15%, and 20%, respectively, and the mass fraction of the water-soluble metal salt potassium chloride was 5% in all powders. The powder mixing process was the same as in Example 1.

[0066] A gradient coating with gradually decreasing Cu content from the substrate to the surface was prepared on a 304 stainless steel substrate using four different powders (one layer of each powder was prepared, with a single layer thickness of 500 μm). The laser additive manufacturing process was standardized as follows: power 800W, scanning speed 10mm / s, and powder feed rate 8g / min.

[0067] The coating was tested according to the method in Test Example 1. The antibacterial rate was 98.3% and the bonding strength was 703 MPa.

[0068] ICP-MS analysis showed that the Cu ion release rate was stable, with a cumulative Cu ion release concentration of 38 μg / L on day 120, indicating a long-lasting protective effect.

[0069] Comparative Example 1

[0070] A coating with a thickness of 500 μm was prepared on a 304 stainless steel substrate using NiCrCo medium-entropy alloy powder with a copper content of 0.5% (the composition of the NiCrCo medium-entropy alloy was the same as in Example 1). The laser additive manufacturing process was as follows: power 500W, scanning speed 10mm / s, powder feed rate 8g / min.

[0071] The test was conducted according to the method in Test Example 1. The bonding strength between the coating and the substrate obtained in Comparative Example 1 was 632 MPa. The antibacterial rate of the 316L stainless steel coating was 94.7%, which was used as the control group.

[0072] The curve of Cu ion release over 120 consecutive days is shown below. Figure 1 .

[0073] As can be seen from the data of Example 1 and Comparative Example 1, the coating prepared in Example 1 has high bonding strength and the ability to inhibit bacterial biofilm formation, effectively disrupting the ecological chain of marine attached organisms and thus inhibiting their attachment. Compared with Comparative Example 1, the addition of Cu and soluble metal salts in Example 1 significantly improves the coating bonding strength and antibacterial rate.

[0074] Example 3

[0075] A series of composite powders were prepared using 316L stainless steel containing 2 wt.% Cu and copper chloride. Gradient coatings (5 layers) were then applied to the surface of a 304 stainless steel substrate. The compositions of the five composite powders used were as follows (the first layer was in contact with the substrate):

[0076] Layer 1: 316L containing 2 wt.% Cu: 92 wt.%, CuCl2: 8 wt.%;

[0077] Layer 2: 316L containing 2 wt.% Cu: 84 wt.%, CuCl2: 16 wt.%;

[0078] Layer 3: 316L containing 2 wt.% Cu: 76 wt.%, CuCl2: 24 wt.%;

[0079] Layer 4: 316L containing 2 wt.% Cu: 68 wt.%, CuCl2: 32 wt.%;

[0080] Layer 5: 316L containing 2 wt.% Cu: 60 wt.%, CuCl2: 40 wt.%.

[0081] The laser additive manufacturing conditions include: laser power 800W, scanning speed 10mm / s, and powder feed rate 12g / min.

[0082] The salt (CuCl2) content in the resulting gradient coating decreased from 40 wt.% at the surface to 8 wt.% at the substrate interface, with the salt content decreasing by 8 wt% with each layer; the thickness of each layer was 0.4 mm.

[0083] The coating bonding strength was 528 MPa when tested according to the method in Test Example 1; the antibacterial test results showed that the antibacterial rate reached 85%.

[0084] Comparative Example 2

[0085] Composite powder was prepared using 316L stainless steel containing 2 wt.% Cu, and a copper-containing stainless steel coating was prepared on the surface of a 304 stainless steel substrate. The laser additive manufacturing conditions included: laser power 800W, scanning speed 10mm / s, and powder feed rate 12g / min.

[0086] The coating adhesion strength was 501 MPa when tested according to the method in Test Example 1; the antibacterial test results showed an antibacterial rate of 80.2%.

[0087] As can be seen from the data of Example 3 and Comparative Example 2, adding soluble copper chloride can effectively improve the bonding strength and antibacterial rate of the coating.

[0088] Example 4

[0089] A coating was prepared on the surface of a 304 stainless steel substrate using a mixed powder of Ti-6Al-4V (doped with 1.5 wt.% Ag nanowires, i.e. Ag titanium alloy powder) and magnesium bromide. The mixed powder consisted of 90 wt.% Ag titanium alloy powder and 10 wt.% MgBr2 powder.

[0090] Two coating layers were prepared, each with a thickness of 0.5 mm. The laser additive manufacturing process was as follows: power 800 W, scanning speed 15 mm / s, powder feed rate 2.4 g / min.

[0091] The coating was tested according to the method in Test Example 1, and the antibacterial rate against Pseudomonas aeruginosa was found to be 82.3%.

[0092] The coating adhesion strength obtained by testing was 351 MPa, and the cumulative Ag ion release concentration after 14 days was measured by ICP-MS to be 1.4 μg / L.

[0093] Comparative Example 3

[0094] A coating was prepared on the surface of a 304 stainless steel substrate using Ti-6Al-4V (doped with 1.5 wt.% Ag nanowires).

[0095] The coating laser additive manufacturing process is the same as in Example 4. A total of two coating layers are prepared, with a single layer thickness of 0.5 mm.

[0096] The coating was tested according to the method in Test Example 1, and the antibacterial rate against Pseudomonas aeruginosa was found to be 74.6%.

[0097] The tested coating adhesion strength was 325 MPa; the cumulative Ag ion release concentration after 14 days was measured by ICP-MS to be 0.8 μg / L.

[0098] Example 5

[0099] Composite materials were prepared using a mixture of AlSi10Mg (with 3 wt.% Zn powder added) and strontium chloride powder. The composition of the mixture was: 95 wt.% AlSi10Mg with added Zn powder and 5 wt.% SrCl2.

[0100] Powder-spread laser additive manufacturing uses 304 stainless steel as the substrate. The process involves a power of 150 W and a scanning speed of 1000 mm / s. 400 layers are printed, each 50 μm thick, to produce a metal-based self-polishing, anti-fouling composite material with dimensions of 20 mm. 20 20 mm 3 .

[0101] The test was conducted according to the method in Test Example 1, and the antibacterial rate of the metal-based self-polishing antifouling composite material against Pseudomonas aeruginosa was found to be 75.2%.

[0102] The tensile properties were tested, and the yield strength of the composite material was found to be 150 MPa.

[0103] ICP-MS analysis showed that the cumulative Zn ion release concentration over 14 days was 3.3 μg / L.

[0104] Comparative Example 4

[0105] Composite materials were prepared using AlSi10Mg (with 3 wt.% Zn powder added).

[0106] The powder-spreading laser additive manufacturing process is the same as in Example 5, using 304 stainless steel as the substrate, with a power of 150 W, a scanning speed of 1000 mm / s, printing 400 layers with a layer thickness of 50 μm, and producing a material with a size of 20. 20 20 mm 3 .

[0107] The test was conducted according to the method in Test Example 1, and the antibacterial rate of the metal-based self-polishing antifouling composite material against Pseudomonas aeruginosa was found to be 70%.

[0108] The tensile properties were tested, and the yield strength of the composite material was 128 MPa.

[0109] ICP-MS measured the Zn ion release concentration at 2.1 μg / L after 14 days.

[0110] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, not all embodiments. People can obtain other embodiments based on the present invention without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A metal-based self-polishing antifouling composite material, characterized by, consists of the following components by mass fraction: 0.5-20% of a metal bacteriostatic agent, 0.5-40% of a water-soluble metal salt, and the balance of a metal alloy powder; The water-soluble metal salt includes one or more of barium acetate, barium bromide, barium chlorate, barium chloride, barium iodide, calcium chloride, calcium bromide, cobalt bromide, cobalt chloride, potassium chloride, scandium sulfate, lithium molybdate, magnesium chloride, magnesium bromide, sodium chloride, nickel chloride, nickel bromide, nickel iodide, rubidium bromide, strontium chloride, copper chloride, and yttrium chloride.

2. The composite material of claim 1, wherein, The metal bacteriostatic agent includes one or more of copper, zinc, and silver.

3. The composite material of claim 1, wherein, The metal alloy powder is a powder prepared from a metal alloy material, and the metal alloy material includes one or more of stainless steel, copper alloy, titanium alloy, aluminum alloy, high-temperature alloy, high-entropy alloy, and amorphous alloy.

4. The composite material of claim 1, wherein, The metal bacteriostatic agent is 1-4% of the mass of the metal alloy powder; and the mass ratio of the sum of the mass of the metal alloy powder and the mass of the metal bacteriostatic agent to the mass of the water-soluble metal salt is 60-95:5-40.

5. The method of producing a metal-based self-polishing antifouling composite material according to any one of claims 1 to 4, characterized in that, The method comprises the following steps: Mixing the metal bacteriostatic agent, the water-soluble metal salt, and the metal alloy powder to obtain the metal-based self-polishing antifouling composite material.

6. A metal-based self-polishing antifouling coating, characterized in that, The coating is made of the metal-based self-polishing antifouling composite material according to any one of claims 1-4 or the metal-based self-polishing antifouling composite material obtained by the preparation method of claim 5.

7. The method of producing a metal-based self-polishing antifouling coating according to claim 6, characterized in that, The method comprises the following steps: Using the composite material to perform laser additive manufacturing on the surface of a substrate to form a metal-based self-polishing antifouling coating on the surface of the substrate; The composite material is the metal-based self-polishing antifouling composite material according to any one of claims 1-4 or the metal-based self-polishing antifouling composite material obtained by the preparation method of claim 5.

8. The preparation method according to claim 7, characterized in that, The conditions of the laser additive manufacturing include a power of 400-8000 W, a scanning speed of 5-1000 mm / s, and a powder feeding rate of 2-30 g / min.

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