CN117004260A - Biofouling-preventing functional coating, and preparation method and application thereof - Google Patents

Abstract

The invention provides a biofouling prevention functional coating, a preparation method and application thereof. According to the biofouling-preventing functional coating, the porous structure is distributed in the coating, polygonal particles are filled in the porous structure, the element composition of the polygonal particles comprises Cu and Ga, the adhesion rate of sulfate reducing bacteria is reduced by the cooperation of the Cu and the Ga, and the biofouling-preventing functional coating has a good antifouling effect. Meanwhile, the biofouling-preventing functional coating has unique antibacterial and nontoxic properties, has potential application potential in the aspect of antifouling, and does not pollute the marine environment. The invention also provides a preparation method and application of the biofouling-preventing functional coating.

Description

An anti-biofouling functional coating and its preparation method and application

Technical field

The invention belongs to the technical field of coatings, and specifically relates to an anti-biofouling functional coating and its preparation method and application.

Background technique

Titanium alloy has the advantages of light weight, good mechanical properties, low density, corrosion resistance, high strength, etc. It is known as "marine metal" and has broad application prospects in the marine environment. However, titanium alloys have serious biofouling problems due to their good biocompatibility. Most marine organisms, including microorganisms, can adhere and grow on the surface of titanium alloy materials, leading to the occurrence of biofouling and long-term service. Safety issues have seriously restricted the application of titanium alloys in the marine environment.

In order to reduce the hazards of biofouling of titanium alloys in the marine environment, it is necessary to inhibit the adhesion and growth of microorganisms, and antifouling coatings are a key method to solve this problem. Antifouling coatings mainly include chemical biocidal antifouling coatings, physical protective antifouling coatings, new antifouling coatings, etc. Chemical biocidal antifouling coatings are currently the most commonly used method and can destroy the formation of biofilms. , to prevent the occurrence of biofouling. However, this method has a greater impact on marine environmental pollution. Chemical fungicides will cause secondary pollution and destroy the marine ecological environment.

Therefore, there is a need to develop new coatings suitable for marine environments.

Contents of the invention

The present invention aims to solve at least one of the above technical problems existing in the prior art. To this end, the present invention provides an anti-biofouling functional coating. The element composition of the coating includes Cu and Ga. Cu and Ga synergistically reduce the adhesion rate of sulfate-reducing bacteria and achieve a good anti-fouling effect. .

The invention also provides a method for preparing an anti-biofouling functional coating.

The invention also provides an application of an anti-biofouling functional coating.

A first aspect of the present invention provides an anti-biofouling functional coating. A porous structure is distributed in the anti-biofouling functional coating. The porous structure is filled with polygonal particles. The polygonal particles are The elemental composition includes Cu and Ga.

One of the technical solutions of the present invention regarding the anti-biofouling functional coating has at least the following beneficial effects:

The anti-biofouling functional coating of the present invention has a porous structure distributed therein, the porous structure is filled with polygonal particles, and the elemental composition of the polygonal particles includes Cu and Ga. On the one hand, the particles are polygonal, and the polygonal structure is conducive to preventing the attachment of microorganisms; on the other hand, the elemental composition of the polygonal particles includes Cu and Ga. Cu and Ga synergistically reduce the attachment rate of sulfate-reducing bacteria, making the coating have good antifouling effect.

The anti-biofouling functional coating of the present invention has unique antibacterial and non-toxic properties, has potential application potential in anti-fouling, and will not cause pollution to the marine environment.

According to some embodiments of the present invention, the composition of the polygonal particles includes Cu, Cu ₂₊₁ O and Cu ₉ Ga ₄ .

Cu, Cu ₂₊₁ O and Cu ₉ Ga ₄ synergistically reduce the adhesion rate of sulfate-reducing bacteria, ensuring that the anti-biofouling functional coating has a good anti-fouling effect.

According to some embodiments of the present invention, the thickness of the anti-biofouling functional coating is 5 μm to 10 μm.

A second aspect of the present invention provides a method for preparing the anti-biofouling functional coating. The method includes: sealing the surface of the pretreated metal substrate with a liquid metal suspension. , after drying and oxidation, react in a metal salt solution to form the anti-biofouling functional coating. The liquid metal includes at least one of gallium liquid metal, gallium indium liquid metal and gallium indium tin liquid metal. , the metal salt solution includes at least one of copper sulfate solution, copper chloride solution, silver sulfate solution and silver chloride solution.

One technical solution of the present invention regarding the preparation method of an anti-biofouling functional coating has at least the following beneficial effects:

In the preparation method of the anti-biofouling functional coating of the present invention, the surface of the metal substrate that has been pretreated, sealed, and dried and oxidized is reacted in a metal salt solution, which is a spontaneous galvanic replacement reaction. Liquid metal serves as the electron donor, and the metal ions in the metal salt solution serve as the electron acceptor. The standard reduction potentials of the two are quite different. Therefore, the reaction will occur spontaneously. The preparation method is simple, and the antifouling coating can be completed at room temperature. The preparation simplifies the preparation process.

The preparation method of the present invention does not require expensive equipment and complex process control, the reaction conditions are not harsh, raw materials are easily available, the production cost is low, and industrial production is easy.

According to some embodiments of the present invention, the pretreatment includes grinding, polishing, cleaning and oxidation in sequence.

During preprocessing:

The function of grinding is to remove impurities and oxides from the surface of the metal substrate, which facilitates subsequent oxidation treatment.

The function of polishing is to further remove impurities and oxides on the surface of the metal substrate, which facilitates subsequent oxidation treatment.

The function of cleaning is to ensure the smoothness of the surface of the metal substrate so that the formed coating is complete and defect-free.

The oxidation treatment method can be micro-arc oxidation. The function of oxidation treatment is to improve the corrosion resistance of metal substrates.

Micro-arc oxidation is a technology that directly grows a ceramic layer on the metal surface in situ. The film obtained through micro-arc oxidation not only has the advantages of strong adhesion and good corrosion resistance, but also can greatly improve the hardness and resistance of the surface. It has abrasion resistance, electrical insulation and other properties, which can play a very good protective role on the substrate. The surface of the metal substrate that has been subjected to micro-arc oxidation will produce porous structures. In the preparation method of the present invention, for these porous structures, these porous structures are first sealed with a suspension of liquid metal. On the one hand, the sealing treatment can reduce The attachment of microorganisms in the pores; on the other hand, liquid metal can be filled into the porous structure through pore sealing treatment. The liquid metal serves as the electron donor, and the metal ions in the subsequent metal salt solution serve as the electron acceptor. The comparison between the two The large standard reduction potential difference causes the liquid metal to undergo a spontaneous galvanic replacement reaction with the metal ions in the metal salt solution, thereby forming polygonal particles and filling the porous structure.

According to some embodiments of the invention, the metal substrate includes titanium alloy.

Titanium alloy has the characteristics of light weight, high strength, good fatigue performance, and certain corrosion resistance under high temperature conditions. It is widely used in aviation, aerospace, shipbuilding and other fields. However, in seawater and marine atmospheric corrosive environments, due to the high potential of titanium alloys, galvanic corrosion will occur when used in contact with dissimilar metals. Micro-arc oxidation technology is an effective measure to solve this problem and an effective surface treatment method to improve the performance of titanium alloys. However, micro-arc oxidation coating is an arc discharge on the surface of the workpiece under the action of high voltage. There are a large number of discharge channels in the resulting oxidation coating, resulting in a large number of micron-scale micropores in the micro-arc oxidation coating. In a corrosive environment, the existence of these micropores not only provides channels for corrosive media to penetrate into the substrate, but also accelerates the rate at which it erodes the substrate. Therefore, it is necessary to further process the oxide coating to isolate the substrate from the external environmental medium. contact to increase its anti-corrosion properties. The present invention uses the spontaneous galvanic replacement reaction of liquid metal and metal salt solution on the surface of a metal substrate that has undergone micro-arc oxidation to form polygonal particles and fill micropores, thereby obtaining an anti-biofouling functional coating with good performance.

According to some embodiments of the present invention, the titanium alloy includes TC4, TA9, TA9-1 and TA10.

According to some embodiments of the invention, the titanium alloy is TC4.

According to some embodiments of the present invention, the preparation method of the liquid metal suspension is: adding the liquid metal to an alcohol solution and performing ultrasonic treatment.

According to some embodiments of the invention, the liquid metal is gallium liquid metal.

According to some embodiments of the present invention, the concentration of the liquid metal suspension is 0.2 mol/L to 0.5 mol/L.

According to some embodiments of the present invention, the alcohol solution includes at least one of methanol, ethanol or ethylene glycol.

According to some embodiments of the invention, the alcohol solution is ethanol.

According to some embodiments of the present invention, the ultrasonic treatment can be performed by an ultrasonic cell disrupter.

According to some embodiments of the present invention, the ultrasonic treatment time is 0.1h to 1h.

According to some embodiments of the present invention, the ultrasonic treatment time is 0.1h to 0.5h.

According to some embodiments of the present invention, the ultrasonic treatment time may be 0.5 h.

According to some embodiments of the present invention, the sealing treatment method is as follows: applying droplets of liquid metal suspension to the surface of the pretreated metal substrate, moving the entire sample block into a vacuum container, letting it stand, and repeating for many times. Second-rate.

According to some embodiments of the present invention, during the sealing process, the vacuum degree may be 5×10 ^-3 Pa.

According to some embodiments of the present invention, during the sealing process, the standing time may be 5 minutes.

According to some embodiments of the present invention, the number of repetitions may be 4 times.

The function of sealing is to reduce the adhesion of microorganisms in the holes.

According to some embodiments of the present invention, the temperature of the dry oxidation is 40°C to 80°C.

According to some embodiments of the present invention, the temperature of the dry oxidation is 40°C to 60°C.

According to some embodiments of the present invention, the temperature of the dry oxidation may be 60°C.

According to some embodiments of the present invention, the drying and oxidation time is 3h to 5h.

According to some embodiments of the present invention, the drying and oxidation time may be 4 hours.

Compared with dry oxidation, oxidation during pretreatment is to improve the corrosion resistance of the metal substrate, while dry oxidation is to increase the bonding strength between the liquid metal and the substrate.

According to some embodiments of the present invention, the concentration of the metal salt solution is 0.1 mol/L to 1 mol/L.

According to some embodiments of the present invention, the concentration of the metal salt solution is 0.1 mol/L to 0.5 mol/L.

According to some embodiments of the present invention, the concentration of the metal salt solution may be about 0.1 mol/L.

According to some embodiments of the present invention, the metal salt solution is a copper sulfate solution.

According to some embodiments of the present invention, the reaction time is 0.1h to 1h.

According to some embodiments of the present invention, the reaction time is 0.1h to 0.5h.

According to some embodiments of the present invention, the reaction time may be about 0.5 h.

The third aspect of the present invention provides the application of the anti-biofouling functional coating in marine equipment.

The present invention relates to a technical solution for the application of anti-biofouling functional coatings in marine equipment, which at least has the following beneficial effects:

Since copper and gallium can synergistically reduce the adhesion rate of sulfate-reducing bacteria, the anti-biofouling functional coating of the present invention can exert a good anti-fouling effect when applied to marine equipment, and has unique antibacterial and non-toxic properties. , environmentally friendly.

According to some embodiments of the present invention, marine equipment includes marine transportation equipment, marine scientific research equipment, marine development equipment and marine protection equipment.

Marine transportation equipment mainly refers to various types of ships. According to the purpose of the ship, there are civilian ships and military ships; according to the hull material, there are wooden ships, steel ships, cement ships and fiberglass ships, etc.; according to the navigation area, there are ocean-going ships, offshore ships, coastal ships and inland river ships, etc.; According to the power device, there are steam engine ships, internal combustion engine ships, steam turbine ships, electric ships and nuclear power ships, etc.; according to the propulsion method, there are paddle ships, propeller ships, flat-rotating propellers and sail-assisted ships, etc.; according to the navigation method, there are Self-propelled ships and non-self-propelled ships; according to navigation status, there are displacement ships and non-displacement ships. Titanium alloy has the advantages of light weight, good mechanical properties, low density, corrosion resistance, high strength, etc. As a ship material, it has broad application prospects. However, titanium alloys have serious biofouling problems due to their good biocompatibility. Most marine organisms, including microorganisms, can adhere and grow on the surface of titanium alloy materials, leading to the occurrence of biofouling and long-term service. Safety issues have seriously restricted the application of titanium alloys in the marine environment. When the coating of the present invention is applied to the surface of a titanium alloy material, the adhesion and growth of marine organisms on the surface of the titanium alloy material can be avoided and the occurrence of biological fouling can be prevented.

Marine scientific research equipment mainly refers to various types of equipment specially used for scientific surveys and experimental activities such as marine resources and environment. Its main carriers are ocean surveying and marine scientific research ships, as well as equipment arranged on the shore, sea surface, underwater, and seabed. Various types of observation and testing equipment. When the coating of the present invention is used on the surface of marine scientific research equipment, it can avoid the adhesion and growth of marine organisms on the surface of titanium alloy materials and prevent the occurrence of biological fouling.

Marine development equipment mainly refers to equipment used in the development of marine oil and gas resources, marine biological resources, marine new energy, and deep-sea solid mineral resources, as well as new marine space resource utilization equipment and seawater resources comprehensive utilization equipment. When the coating of the present invention is used on the surface of marine development equipment, it can avoid the adhesion and growth of marine organisms on the surface of titanium alloy materials and prevent the occurrence of biological fouling.

Marine protection equipment mainly refers to marine rights protection equipment such as maritime surveillance ships, coast patrol ships, and coast guard ships; marine support equipment such as emergency rescue ships and salvage ships; and marine environmental protection equipment such as oil spill recovery ships and marine garbage recovery devices. When the coating of the present invention is used to protect the surface of marine equipment, it can also prevent the adhesion and growth of marine organisms on the surface of titanium alloy materials and prevent the occurrence of biological fouling.

Description of the drawings

Figure 1 is a schematic diagram of the preparation process of the coating of Example 1.

Figure 2 is the surface micromorphology of the anti-biofouling functional coating prepared in Example 1.

Figure 3 is an X-ray diffraction pattern of the anti-biofouling functional coating prepared in Example 1.

Figure 4 shows the test results of the anti-sulfate reducing bacteria adhesion performance of the coatings prepared in TC4 sample, Example 1 and Comparative Examples 1-2.

Detailed ways

The following are specific examples of the present invention, and the technical solutions of the present invention are further described in conjunction with the examples, but the present invention is not limited to these examples.

In some embodiments of the present invention, the present invention provides an anti-biofouling functional coating. A porous structure is distributed in the anti-biofouling functional coating. The porous structure is filled with polygonal particles. The elements of the polygonal particles are The composition includes Cu and Ga.

It can be understood that the anti-biofouling functional coating of the present invention has a porous structure distributed therein, and the porous structure is filled with polygonal particles, and the elemental composition of the polygonal particles includes Cu and Ga. On the one hand, the particles are polygonal, and the polygonal structure is conducive to preventing the attachment of microorganisms; on the other hand, the elemental composition of the polygonal particles includes Cu and Ga. Cu and Ga synergistically reduce the attachment rate of sulfate-reducing bacteria, making the coating have good antifouling effect.

The anti-biofouling functional coating of the present invention has unique antibacterial and non-toxic properties, has potential application potential in anti-fouling, and will not cause pollution to the marine environment.

In some embodiments of the invention, the composition of the polygonal particles includes Cu, Cu ₂₊₁ O, and Cu ₉ Ga ₄ .

Cu, Cu ₂₊₁ O and Cu ₉ Ga ₄ synergistically reduce the adhesion rate of sulfate-reducing bacteria, ensuring that the anti-biofouling functional coating has a good anti-fouling effect.

Cu ₂₊₁ O is metal excess type Cu ₂ O.

In some embodiments of the present invention, the thickness of the anti-biofouling functional coating is 5 μm to 10 μm.

In other embodiments of the present invention, the present invention provides a method for preparing an anti-biofouling functional coating. The method includes: sealing the surface of a pretreated metal substrate with a liquid metal suspension. After treatment, drying and oxidation, reaction is carried out in a metal salt solution to form an anti-biofouling functional coating. The liquid metal includes at least one of gallium liquid metal, gallium indium liquid metal and gallium indium tin liquid metal. The metal salt solution Including at least one of copper sulfate solution, copper chloride solution, silver sulfate solution and silver chloride solution.

It can be understood that the preparation method of the anti-biofouling functional coating of the present invention is a spontaneous galvanic replacement reaction in which the surface of the metal substrate that has been pretreated, sealed, and dried and oxidized is reacted in a metal salt solution. Liquid metal serves as the electron donor, and the metal ions in the metal salt solution serve as the electron acceptor. The standard reduction potentials of the two are quite different. Therefore, the reaction will occur spontaneously. The preparation method is simple, and the antifouling coating can be completed at room temperature. The preparation simplifies the preparation process.

The preparation method of the present invention does not require expensive equipment and complex process control, the reaction conditions are not harsh, raw materials are easily available, the production cost is low, and industrial production is easy.

In some embodiments of the present invention, the pretreatment includes grinding, polishing, cleaning and oxidation in sequence.

It should be noted that during the preprocessing process:

The function of grinding is to remove impurities and oxides from the surface of the metal substrate, which facilitates subsequent oxidation treatment.

The function of polishing is to further remove impurities and oxides on the surface of the metal substrate, which facilitates subsequent oxidation treatment.

The function of cleaning is to ensure the smoothness of the surface of the metal substrate so that the formed coating is complete and defect-free.

The oxidation treatment method can be micro-arc oxidation. The function of oxidation treatment is to improve the corrosion resistance of metal substrates.

Micro-arc oxidation is a technology that directly grows a ceramic layer on the metal surface in situ. The film obtained through micro-arc oxidation not only has the advantages of strong adhesion and good corrosion resistance, but also can greatly improve the hardness and resistance of the surface. It has abrasion resistance, electrical insulation and other properties, which can play a very good protective role on the substrate. The surface of the metal substrate that has been subjected to micro-arc oxidation will produce porous structures. In the preparation method of the present invention, for these porous structures, these porous structures are first sealed with a suspension of liquid metal. On the one hand, the sealing treatment can reduce The attachment of microorganisms in the pores; on the other hand, liquid metal can be filled into the porous structure through pore sealing treatment. The liquid metal serves as the electron donor, and the metal ions in the subsequent metal salt solution serve as the electron acceptor. The comparison between the two The large standard reduction potential difference causes the liquid metal to undergo a spontaneous galvanic replacement reaction with the metal ions in the metal salt solution, thereby forming polygonal particles and filling the porous structure.

In some embodiments of the invention, the metal substrate includes titanium alloy.

Titanium alloy has the characteristics of light weight, high strength, good fatigue performance, and certain corrosion resistance under high temperature conditions. It is widely used in aviation, aerospace, shipbuilding and other fields. However, in seawater and marine atmospheric corrosive environments, due to the high potential of titanium alloys, galvanic corrosion will occur when used in contact with dissimilar metals. Micro-arc oxidation technology is an effective measure to solve this problem and an effective surface treatment method to improve the performance of titanium alloys. However, micro-arc oxidation coating is an arc discharge on the surface of the workpiece under the action of high voltage. There are a large number of discharge channels in the resulting oxidation coating, resulting in a large number of micron-scale micropores in the micro-arc oxidation coating. In a corrosive environment, the existence of these micropores not only provides channels for corrosive media to penetrate into the substrate, but also accelerates the rate at which it erodes the substrate. Therefore, it is necessary to further process the oxide coating to isolate the substrate from the external environmental medium. contact to increase its anti-corrosion properties. The present invention uses the spontaneous galvanic replacement reaction of liquid metal and metal salt solution on the surface of a metal substrate that has undergone micro-arc oxidation to form polygonal particles and fill micropores, thereby obtaining an anti-biofouling functional coating with good performance.

In some embodiments of the invention, titanium alloys include TC4, TA9, TA9-1, and TA10.

In some embodiments of the invention, the titanium alloy is TC4.

In some embodiments of the present invention, the preparation method of the liquid metal suspension is: adding the liquid metal to the alcohol solution and performing ultrasonic treatment.

In some embodiments of the invention, the liquid metal is gallium liquid metal.

In some embodiments of the present invention, the concentration of the liquid metal suspension is 0.2 mol/L to 0.5 mol/L.

In some embodiments of the invention, the alcohol solution includes at least one of methanol, ethanol or ethylene glycol.

In some embodiments of the invention, the alcohol solution is ethanol.

In some embodiments of the invention, sonication can be performed by an ultrasonic cell disrupter.

In some embodiments of the present invention, the time of ultrasonic treatment is 0.1h to 1h.

In some embodiments of the present invention, the time of ultrasonic treatment is 0.1h to 0.5h.

In some embodiments of the present invention, the time of ultrasonic treatment may be 0.5 h.

In some embodiments of the present invention, the method of sealing treatment is: apply droplets of liquid metal suspension to the surface of the pretreated metal substrate, move the entire sample block into a vacuum container, let it stand, and repeat several times .

In some embodiments of the present invention, during the sealing process, the vacuum degree may be 5×10 ^-3 Pa.

In some embodiments of the present invention, during the hole sealing process, the standing time may be 5 minutes.

In some embodiments of the present invention, the number of repetitions may be 4 times.

It should be noted that the function of sealing is to reduce the adhesion of microorganisms in the holes.

In some embodiments of the present invention, the temperature of dry oxidation is 40°C to 80°C.

In some embodiments of the present invention, the temperature of dry oxidation is 40°C to 60°C.

In some embodiments of the present invention, the temperature of dry oxidation may be 60°C.

In some embodiments of the present invention, the drying and oxidation time is 3h to 5h.

In some embodiments of the present invention, the drying and oxidation time may be 4 hours.

Compared with dry oxidation, oxidation during pretreatment is to improve the corrosion resistance of the metal substrate, while dry oxidation is to increase the bonding strength between the liquid metal and the substrate.

In some embodiments of the present invention, the concentration of the metal salt solution is 0.1 mol/L ~ 1 mol/L.

In some embodiments of the present invention, the concentration of the metal salt solution is 0.1 mol/L to 0.5 mol/L.

In some embodiments of the present invention, the concentration of the metal salt solution may be about 0.1 mol/L.

In some embodiments of the invention, the metal salt solution is a copper sulfate solution.

In some embodiments of the present invention, the reaction time is 0.1h to 1h.

In some embodiments of the present invention, the reaction time is 0.1h to 0.5h.

In some embodiments of the present invention, the reaction time may be about 0.5 h.

In other embodiments of the present invention, the present invention provides applications of anti-biofouling functional coatings in marine equipment.

It can be understood that the anti-biofouling functional coating of the present invention, because copper and gallium ions can synergistically reduce the adhesion rate of sulfate-reducing bacteria, can exert a good anti-fouling effect when applied to marine equipment, and has unique antibacterial properties. And non-toxic properties, environmentally friendly.

In some embodiments of the present invention, marine equipment includes marine transportation equipment, marine scientific research equipment, marine development equipment, and marine protection equipment.

Among them, marine transportation equipment mainly refers to various types of ships. According to the purpose of the ship, there are civilian ships and military ships; according to the hull material, there are wooden ships, steel ships, cement ships and fiberglass ships, etc.; according to the navigation area, there are ocean-going ships, offshore ships, coastal ships and inland river ships, etc.; According to the power device, there are steam engine ships, internal combustion engine ships, steam turbine ships, electric ships and nuclear power ships, etc.; according to the propulsion method, there are paddle ships, propeller ships, flat propellers and sail navigation ships, etc.; according to the navigation method, there are Self-propelled ships and non-self-propelled ships; according to navigation status, there are displacement ships and non-displacement ships. Titanium alloy has the advantages of light weight, good mechanical properties, low density, corrosion resistance, high strength, etc. It has broad application prospects as a ship material. However, titanium alloys have serious biofouling problems due to their good biocompatibility. Most marine organisms, including microorganisms, can adhere and grow on the surface of titanium alloy materials, leading to the occurrence of biofouling and long-term service. Safety issues have seriously restricted the application of titanium alloys in the marine environment. When the coating of the present invention is applied to the surface of a titanium alloy material, the adhesion and growth of marine organisms on the surface of the titanium alloy material can be avoided and the occurrence of biological fouling can be prevented.

Marine scientific research equipment mainly refers to various types of equipment specially used for scientific surveys and experimental activities such as marine resources and environment. Its main carriers are ocean surveying and marine scientific research ships, as well as equipment arranged on the shore, sea surface, underwater, and seabed. Various types of observation and testing equipment. When the coating of the present invention is used on the surface of marine scientific research equipment, it can avoid the adhesion and growth of marine organisms on the surface of titanium alloy materials and prevent the occurrence of biological fouling.

Marine development equipment mainly refers to equipment used in the development of marine oil and gas resources, marine biological resources, marine new energy, and deep-sea solid mineral resources, as well as new marine space resource utilization equipment and seawater resources comprehensive utilization equipment. When the coating of the present invention is used on the surface of marine development equipment, it can avoid the adhesion and growth of marine organisms on the surface of titanium alloy materials and prevent the occurrence of biological fouling.

Marine protection equipment mainly refers to marine rights protection equipment such as maritime surveillance ships, coast patrol ships, and coast guard ships; marine support equipment such as emergency rescue ships and salvage ships; and marine environmental protection equipment such as oil spill recovery ships and marine garbage recovery devices. When the coating of the present invention is used to protect the surface of marine equipment, it can also prevent the adhesion and growth of marine organisms on the surface of titanium alloy materials and prevent the occurrence of biological fouling.

The technical solutions of the present invention will be better understood below in conjunction with specific embodiments.

Example 1

This embodiment provides an anti-biofouling functional coating. A porous structure is distributed in the coating. The porous structure is filled with polygonal particles. The elemental composition of the polygonal particles includes Cu and Ga.

The specific preparation method includes the following steps:

(1) Grind, polish, and clean the titanium alloy TC4 substrate in order to remove the oxide film and oil stains on its surface, and then suspend the sample in the electrolyte for micro-arc oxidation treatment to obtain corrosion-resistant and porous Titanium dioxide oxide layer (denoted as TC4-MAO).

Among them, the voltage of micro-arc oxidation treatment is 260V, the duty cycle is 30%, the frequency is 300HZ, and the oxidation time is 15min.

(2) Add 0.4g of gallium-based liquid metal to 15mL of ethanol solution, and conduct ultrasonic treatment for 30 minutes under the action of an ultrasonic cell disrupter to obtain a suspension of gallium liquid metal particles with a diameter of about 400nm.

(3) Take 200 μL of the gallium liquid metal particle suspension prepared in step (2), dropwise apply it onto the surface of TC4-MAO prepared in step (1), and move the entire sample block into a vacuum container with a vacuum degree of 5× 10 ^-3 Pa, let stand for 5 minutes.

(4) Repeat step (3) 4 times, then rinse the remaining gallium liquid metal particles on the surface with ethanol, and dry and oxidize them at 60°C for 4 hours to obtain a liquid metal sealed titanium alloy coating (denoted as TC4-MAO- LM).

(5) Immerse the TC4-MAO-LM sample block prepared in step (4) into 0.1 mol/L CuSO ₄ solution, let it stand for 30 minutes, take out the sample block, rinse the surface with deionized water, and dry at 60°C for 1 hour , an anti-biofouling functional coating (denoted as TC4-MAO-LMCu) was obtained.

Comparative example 1

This comparative example provides a functional coating.

The specific preparation method is:

The titanium alloy TC4 substrate is ground, polished, and cleaned in sequence to remove the oxide film and oil stains on its surface, and then the sample is suspended in the electrolyte for micro-arc oxidation treatment to obtain a corrosion-resistant and porous titanium dioxide oxide layer. (Denoted as TC4-MAO).

The voltage of micro-arc oxidation treatment is 260V, the duty cycle is 30%, the frequency is 300HZ, and the oxidation time is 15min.

Comparative example 2

This comparative example provides a functional coating.

The specific preparation method is:

(1) Grind, polish, and clean the titanium alloy TC4 substrate in order to remove the oxide film and oil stains on its surface, and then suspend the sample in the electrolyte for micro-arc oxidation treatment to obtain corrosion-resistant and porous Titanium dioxide oxide layer.

The voltage of micro-arc oxidation treatment is 260V, the duty cycle is 30%, the frequency is 300HZ, and the oxidation time is 15min.

(2) Add 0.4g of gallium-based liquid metal to 15mL of ethanol solution, and conduct ultrasonic treatment for 30 minutes under the action of an ultrasonic cell disrupter to obtain a suspension of gallium liquid metal particles with a diameter of about 400nm.

(3) Take 200 μL of the suspension prepared in step (2), drip it onto the surface of TC4-MAO prepared in step (1), and move the entire block into a vacuum container with a vacuum degree of 5×10 ^-3 Pa , let stand for 5 minutes.

(4) Repeat step (3) 4 times, then rinse the remaining gallium liquid metal particles on the surface with ethanol, and dry and oxidize them at 60°C for 4 hours to obtain a liquid metal sealed titanium alloy coating (denoted as TC4-MAO- LM).

The above preparation process is shown in Figure 1.

Performance Testing

Figure 2 is a micromorphology diagram of the surface of the coating prepared in Example 1.

As can be seen from Figure 2, the anti-biofouling functional coating prepared in Example 1 is distributed with porous structures, and these porous structures are filled with polygonal particles.

The coating prepared in Example 1 was characterized by X-ray powder diffraction, and the results are shown in Figure 3.

According to Figure 3, it can be seen that there are five crystal structures of Ti, TiO ₂ , Cu, Cu ₂₊₁ O, and Cu ₉ Ga ₄ in the coating, indicating that there are Cu and Ga in the coating, and the components of the polygonal particles include Cu, Cu ₂₊₁ O and Cu ₉ Ga ₄ .

Figure 4 is a test chart of the anti-sulfate reducing bacteria adhesion performance of untreated TC4 samples, coatings prepared in Example 1 and Comparative Examples 1-2. As can be seen from Figure 4, after 14 days of immersion in artificial seawater with sulfate-reducing bacteria, the surface SRB adhesion rates of untreated TC4 and TC4-MAO (Comparative Example 1) were 22.89% and 25.91%, respectively. The sulfate reduction The bacteria form a dense biofilm on its surface.

However, the adhesion rates of sulfate-reducing bacteria on the coating surfaces of TC4-MAO-LM (Comparative Example 2) and TC4-MAO-LMCu (Example 1) are only 0.89% and 0.02%, indicating that the TC4-MAO- LMCu coating has good antibacterial properties.

It should be noted that although the antifouling effect of the coating can also be evaluated through different microorganisms. However, those skilled in the art know that the adhesion rate of sulfate-reducing bacteria is sufficient to illustrate the bio-antifouling performance of the coating.

The invention also provides the application of the anti-biofouling functional coating in marine equipment.

It can be understood that the anti-biofouling functional coating of the present invention, because copper and gallium ions can synergistically reduce the adhesion rate of sulfate-reducing bacteria, can exert a good anti-fouling effect when applied to marine equipment, and has unique antibacterial properties. And non-toxic properties, environmentally friendly.

In some embodiments of the present invention, marine equipment includes marine transportation equipment, marine scientific research equipment, marine development equipment, and marine protection equipment.

The present invention has been described in detail with reference to the embodiments above. However, the present invention is not limited to the above-mentioned embodiments. Various changes can be made within the knowledge scope of those of ordinary skill in the art without departing from the spirit of the present invention.

Claims (10)

1. An anti-biofouling functional coating, characterized in that a porous structure is distributed in the anti-biofouling functional coating, the porous structure is filled with polygonal particles, and the elemental composition of the polygonal particles is Includes Cu and Ga. 2. The anti-biofouling functional coating according to claim 1, wherein the components of the polygonal particles include Cu, Cu ₂₊₁ O and Cu ₉ Ga ₄ . 3. The anti-biofouling functional coating according to claim 1 or 2, characterized in that the thickness of the anti-biofouling functional coating is 5 μm to 10 μm. 4. A method for preparing the anti-biofouling functional coating as claimed in any one of claims 1 to 3, characterized in that the method includes: coating the surface of the pretreated metal substrate with liquid metal. The suspension is subjected to hole sealing treatment, and after drying and oxidation, it is reacted in a metal salt solution to form the anti-biofouling functional coating. The liquid metal includes gallium liquid metal, gallium indium liquid metal and gallium indium tin. At least one of liquid metals, the metal salt solution includes at least one of copper sulfate solution, copper chloride solution, silver sulfate solution and silver chloride solution. 5. The method according to claim 4, wherein the pretreatment includes grinding, polishing, cleaning and oxidation in sequence. 6. The method according to claim 4, characterized in that the preparation method of the liquid metal suspension is: adding the liquid metal to an alcohol solution and performing ultrasonic treatment. 7. The method according to claim 4, wherein the drying and oxidation temperature is 40°C to 80°C; and/or the drying and oxidation time is 3h to 5h. 8. The method according to claim 4, wherein the concentration of the metal salt solution is 0.1 mol/L to 1 mol/L. 9. The method according to claim 4, characterized in that the reaction time is 0.1h to 1h. 10. Application of the anti-biofouling functional coating according to any one of claims 1 to 3 in marine equipment.