A kind of anti-biofouling functional coating and its preparation method and application

Abstract

The present invention provides an anti-biofouling functional coating, and a preparation method and application thereof. According to the anti-biofouling functional coating of the present invention, a porous structure is distributed in the coating, and the porous structure is filled with polygonal particles. The element composition of the polygonal particles includes Cu and Ga. Cu and Ga synergistically reduce the attachment rate of sulfate-reducing bacteria and have a good anti-fouling effect. At the same time, 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. The present invention also provides a preparation method and application of the anti-biofouling functional coating.

Description

Technical Field

[0001] The present invention belongs to the technical field of coatings, and in particular relates to an anti-biofouling functional coating and a preparation method and application thereof. Background Art

[0002] 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, due to its good biocompatibility, titanium alloy has serious biofouling problems. Most marine organisms, including microorganisms, can adhere and grow on the surface of titanium alloy materials, leading to biofouling and causing safety problems in long-term service, which seriously restricts the application of titanium alloy in the marine environment.

[0003] In order to reduce the harm of biological fouling of titanium alloy in the marine environment, it is necessary to inhibit the adhesion and growth of microorganisms. Antifouling coating is the key method to solve this problem. Antifouling coating mainly includes chemical biocidal antifouling coating, physical protection antifouling coating, new antifouling coating, etc. Chemical biocidal antifouling coating is the most commonly used method at present, which can destroy the formation of biofilm and prevent the occurrence of biological fouling. However, this method has a great impact on marine environmental pollution. Chemical fungicides will cause secondary pollution and damage the marine ecological environment.

[0004] Therefore, there is a need to develop new coatings suitable for marine environments. Summary of the invention

[0005] The present invention aims to solve at least one of the above-mentioned technical problems existing in the prior art. To this end, the present invention provides an anti-biofouling functional coating, the element composition of which includes Cu and Ga, and Cu and Ga synergistically reduce the attachment rate of sulfate-reducing bacteria, thereby achieving a good antifouling effect.

[0006] The present invention also provides a method for preparing the anti-biofouling functional coating.

[0007] The present invention also provides an application of an anti-biofouling functional coating.

[0008] A first aspect of the present invention provides an anti-biofouling functional coating, wherein a porous structure is distributed in the anti-biofouling functional coating, wherein the porous structure is filled with polygonal particles, wherein the element composition of the polygonal particles includes Cu and Ga.

[0009] One of the technical solutions of the present invention regarding the anti-biofouling functional coating has at least the following beneficial effects:

[0010] 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 element 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 element composition of the polygonal particles includes Cu and Ga, and Cu and Ga synergistically reduce the attachment rate of sulfate-reducing bacteria, so that the coating has a good antifouling effect.

[0011] The anti-biofouling functional coating of the present invention has unique antibacterial and non-toxic properties, has potential application in antifouling, and will not cause pollution to the marine environment.

[0012] According to some embodiments of the present invention, the components of the polygonal particles include Cu, Cu 2+1 O and Cu 9 Ga 4 .

[0013] Cu, Cu 2+1 O and Cu 9 Ga 4 The attachment rate of sulfate-reducing bacteria was synergistically reduced, ensuring that the anti-biofouling functional coating had a good antifouling effect.

[0014] According to some embodiments of the present invention, the anti-biofouling functional coating has a thickness of 5 μm to 10 μm.

[0015] The second aspect of the present invention provides a method for preparing the anti-biofouling functional coating, the method comprising: sealing the pretreated metal substrate surface with a liquid metal suspension, drying and oxidizing, and reacting in a metal salt solution to form the anti-biofouling functional coating, the liquid metal comprising at least one of gallium liquid metal, gallium indium liquid metal and gallium indium tin liquid metal, and the metal salt solution comprising at least one of copper sulfate solution, copper chloride solution, silver sulfate solution and silver chloride solution.

[0016] A technical solution in the method for preparing the anti-biofouling functional coating of the present invention has at least the following beneficial effects:

[0017] The preparation method of the anti-biofouling functional coating of the present invention is to react the surface of the metal substrate after pretreatment, sealing treatment and dry oxidation in a metal salt solution, which is a spontaneous galvanic displacement reaction. The liquid metal is used as an electron donor, and the metal ions in the metal salt solution are used as electron acceptors. The standard reduction potentials of the two are quite different, so they react spontaneously. The preparation method is simple, and the preparation of the antifouling coating can be completed at room temperature, which simplifies the preparation process.

[0018] The preparation method of the present invention does not require expensive equipment and complicated process control, has undemanding reaction conditions, has readily available raw materials, has low production costs, and is easy to industrialize.

[0019] According to some embodiments of the present invention, the pretreatment includes grinding, polishing, cleaning and oxidation treatment performed sequentially.

[0020] During preprocessing:

[0021] The purpose of grinding is to remove impurities and oxides on the surface of the metal substrate, which is conducive to the subsequent oxidation treatment.

[0022] The role of polishing is to further remove impurities and oxides on the surface of the metal substrate, which is conducive to the subsequent oxidation treatment.

[0023] The role of cleaning is to ensure the smoothness of the metal substrate surface and make the formed coating complete and defect-free.

[0024] The oxidation treatment method may be a micro-arc oxidation method. The oxidation treatment is used to improve the corrosion resistance of the metal substrate.

[0025] Micro-arc oxidation is a technology that directly grows a ceramic layer in situ on the metal surface. The film obtained by micro-arc oxidation not only has the advantages of strong adhesion and good corrosion resistance, but also can greatly improve the surface hardness, wear resistance, electrical insulation and other properties, which can play a good protective role on the substrate. The surface of the metal substrate after micro-arc oxidation will produce a porous structure. The preparation method of the present invention, for these porous structures, first uses a suspension of liquid metal to seal these porous structures. On the one hand, the sealing treatment can reduce the attachment of microorganisms in the holes; on the other hand, the sealing treatment can first fill the liquid metal into the porous structure. The liquid metal acts as an electron donor, and the metal ions in the subsequent metal salt solution act as electron acceptors. The large difference in standard reduction potential between the two makes the liquid metal and the metal ions in the metal salt solution undergo a spontaneous electrocouple replacement reaction, thereby forming polygonal particles and filling the porous structure.

[0026] According to some embodiments of the present invention, the metal substrate comprises a titanium alloy.

[0027] 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 the corrosive environment of seawater and marine atmosphere, due to the high potential of titanium alloy, galvanic corrosion will occur when it is 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 alloy. However, the micro-arc oxidation coating is an arc discharge on the surface of the workpiece under high pressure. There are a large number of discharge channels in the obtained oxidation coating, resulting in a large number of micron-scale micropores in the micro-arc oxidation coating. In a corrosive environment, the presence of these micropores not only provides a channel for the corrosive medium to penetrate into the substrate, but also accelerates the speed of its erosion of the substrate. Therefore, it is necessary to further treat the oxidation coating to isolate the substrate from the contact with the external environment medium and increase its anti-corrosion performance. The present invention uses the spontaneous galvanic replacement reaction of liquid metal and metal salt solution on the surface of the metal substrate after micro-arc oxidation to form polygonal particles and fill the micropores, thereby obtaining a functional coating with good performance against biofouling.

[0028] According to some embodiments of the present invention, the titanium alloy includes TC4, TA9, TA9-1 and TA10.

[0029] According to some embodiments of the present invention, the titanium alloy is TC4.

[0030] According to some embodiments of the present invention, the method for preparing the liquid metal suspension is: adding the liquid metal to an alcohol solution and performing ultrasonic treatment.

[0031] According to some embodiments of the present invention, the liquid metal is gallium liquid metal.

[0032] 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.

[0033] According to some embodiments of the invention, the alcohol solution comprises at least one of methanol, ethanol or ethylene glycol.

[0034] According to some embodiments of the invention, the alcohol solution is ethanol.

[0035] According to some embodiments of the present invention, the ultrasonic treatment may be performed by an ultrasonic cell disruptor.

[0036] According to some embodiments of the present invention, the ultrasonic treatment time is 0.1 h to 1 h.

[0037] According to some embodiments of the present invention, the ultrasonic treatment time is 0.1 h to 0.5 h.

[0038] According to some embodiments of the present invention, the ultrasonic treatment time may be 0.5 h.

[0039] According to some embodiments of the present invention, the sealing treatment method is: applying liquid metal suspension droplets to the pretreated surface of the metal substrate, and moving the entire sample into a vacuum container, leaving it to stand, and repeating the process multiple times.

[0040] According to some embodiments of the present invention, the vacuum degree during the sealing process can be 5×10 -3 Pa.

[0041] According to some embodiments of the present invention, during the sealing process, the standing time may be 5 minutes.

[0042] According to some embodiments of the present invention, the number of repetitions may be 4 times.

[0043] The purpose of sealing treatment is to reduce the attachment of microorganisms in the pores.

[0044] According to some embodiments of the present invention, the temperature of the dry oxidation is 40°C to 80°C.

[0045] According to some embodiments of the present invention, the temperature of the dry oxidation is 40°C to 60°C.

[0046] According to some embodiments of the present invention, the temperature of the dry oxidation may be 60°C.

[0047] According to some embodiments of the present invention, the drying and oxidation time is 3 h to 5 h.

[0048] According to some embodiments of the present invention, the drying and oxidation time may be 4 hours.

[0049] 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.

[0050] According to some embodiments of the present invention, the concentration of the metal salt solution is 0.1 mol / L to 1 mol / L.

[0051] 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.

[0052] According to some embodiments of the present invention, the concentration of the metal salt solution may be about 0.1 mol / L.

[0053] According to some embodiments of the present invention, the metal salt solution is a copper sulfate solution.

[0054] According to some embodiments of the present invention, the reaction time is 0.1 h to 1 h.

[0055] According to some embodiments of the present invention, the reaction time is 0.1 h to 0.5 h.

[0056] According to some embodiments of the present invention, the reaction time may be about 0.5 h.

[0057] The third aspect of the present invention provides the use of the anti-biofouling functional coating in marine equipment.

[0058] The present invention provides a technical solution for the application of anti-biofouling functional coating in marine equipment, which has at least the following beneficial effects:

[0059] The anti-biofouling functional coating of the present invention can exert a good antifouling effect when applied to marine equipment because copper and gallium can synergistically reduce the attachment rate of sulfate-reducing bacteria, and has unique antibacterial and non-toxic properties and is environmentally friendly.

[0060] 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.

[0061] Marine transport 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; according to the navigation area, there are ocean-going ships, offshore ships, coastal ships and inland ships; according to the power plant, there are steam ships, internal combustion engine ships, steam turbine ships, electric ships and nuclear-powered ships; according to the propulsion method, there are paddle steamers, propeller ships, flat-rotating propellers and sail-assisted ships; according to the navigation method, there are self-propelled ships and non-self-propelled ships; according to the navigation state, 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., and has broad application prospects as a ship material. However, due to its good biocompatibility, titanium alloy has serious biological fouling problems. Most marine organisms, including microorganisms, can adhere and grow on the surface of titanium alloy materials, resulting in biological fouling, causing safety problems in long-term service, which seriously restricts the application of titanium alloy in the marine environment. When the coating of the present invention is applied to the surface of a titanium alloy material, it can prevent marine organisms from adhering and growing on the surface of the titanium alloy material, thereby preventing the occurrence of biological fouling.

[0062] Marine scientific research equipment mainly refers to various equipment specially used for scientific investigation and experimental activities of marine resources, environment, etc. Its main carriers are marine survey and marine scientific research ships, as well as various observation and detection equipment arranged on the shore, sea surface, underwater and seabed. When the coating of the present invention is used on the surface of marine scientific research equipment, it can prevent the adhesion and growth of marine organisms on the surface of titanium alloy materials, and prevent the occurrence of biological fouling.

[0063] Marine development equipment mainly refers to equipment used for the development of marine oil and gas resources, marine biological resources, marine new energy, deep-sea solid mineral resources, as well as new marine space resource utilization equipment and seawater resource comprehensive utilization equipment. When the coating of the present invention is used on the surface of marine development equipment, it can prevent the adhesion and growth of marine organisms on the surface of titanium alloy materials and prevent the occurrence of biological fouling.

[0064] Marine protection equipment mainly refers to marine monitoring ships, patrol ships, coast guard ships and other marine rights protection equipment, emergency rescue ships, salvage ships and other marine security equipment, as well as oil spill recovery ships, marine garbage recovery equipment and other marine environmental protection equipment. When the coating of the present invention is applied to the surface of marine protection equipment, it can also prevent the adhesion and growth of marine organisms on the surface of titanium alloy materials, thereby preventing the occurrence of biological fouling. BRIEF DESCRIPTION OF THE DRAWINGS

[0065] Figure 1 Schematic diagram of the preparation process of the coating in Example 1.

[0066] Figure 2 This is the surface micromorphology of the anti-biofouling functional coating prepared in Example 1.

[0067] Figure 3 This is the X-ray diffraction pattern of the anti-biofouling functional coating prepared in Example 1.

[0068] Figure 4 These are the test results of the sulfate-reducing bacteria adhesion resistance of the coatings prepared in the TC4 sample, Example 1, and Comparative Examples 1-2. DETAILED DESCRIPTION

[0069] The following are specific embodiments of the present invention, and the technical solutions of the present invention are further described in conjunction with the embodiments, but the present invention is not limited to these embodiments.

[0070] In some embodiments of the present invention, the present invention provides an anti-biofouling functional coating, wherein a porous structure is distributed in the anti-biofouling functional coating, and the porous structure is filled with polygonal particles, and the elemental composition of the polygonal particles includes Cu and Ga.

[0071] 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 element 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 element composition of the polygonal particles includes Cu and Ga, and Cu and Ga synergistically reduce the attachment rate of sulfate-reducing bacteria, so that the coating has a good antifouling effect.

[0072] The anti-biofouling functional coating of the present invention has unique antibacterial and non-toxic properties, has potential application in antifouling, and will not cause pollution to the marine environment.

[0073] In some embodiments of the present invention, the components of the polygonal particles include Cu, Cu 2+1 O and Cu 9 Ga 4 .

[0074] Cu, Cu 2+1 O and Cu 9 Ga 4 The attachment rate of sulfate-reducing bacteria was synergistically reduced, ensuring that the anti-biofouling functional coating had a good antifouling effect.

[0075] Cu 2+1 O is a metal excess type Cu 2 O.

[0076] In some embodiments of the present invention, the anti-biofouling functional coating has a thickness of 5 μm to 10 μm.

[0077] In some other embodiments of the present invention, the present invention provides a method for preparing an anti-biofouling functional coating, the method comprising: sealing the surface of a pretreated metal substrate with a suspension of liquid metal, drying and oxidizing, and reacting in a metal salt solution to form an anti-biofouling functional coating, the liquid metal comprising at least one of gallium liquid metal, gallium indium liquid metal and gallium indium tin liquid metal, and the metal salt solution comprising at least one of copper sulfate solution, copper chloride solution, silver sulfate solution and silver chloride solution.

[0078] It can be understood that the preparation method of the anti-biofouling functional coating of the present invention is that 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 displacement reaction. The liquid metal is used as an electron donor, and the metal ions in the metal salt solution are used as electron acceptors. The standard reduction potentials of the two are quite different, so they react spontaneously. The preparation method is simple, and the preparation of the antifouling coating can be completed at room temperature, which simplifies the preparation process.

[0079] The preparation method of the present invention does not require expensive equipment and complicated process control, has undemanding reaction conditions, has readily available raw materials, has low production costs, and is easy to industrialize.

[0080] In some embodiments of the present invention, the pretreatment includes grinding, polishing, cleaning and oxidation treatment performed sequentially.

[0081] It should be noted that during the preprocessing process:

[0082] The purpose of grinding is to remove impurities and oxides on the surface of the metal substrate, which is conducive to the subsequent oxidation treatment.

[0083] The role of polishing is to further remove impurities and oxides on the surface of the metal substrate, which is conducive to the subsequent oxidation treatment.

[0084] The role of cleaning is to ensure the smoothness of the metal substrate surface and make the formed coating complete and defect-free.

[0085] The oxidation treatment method may be a micro-arc oxidation method. The oxidation treatment is used to improve the corrosion resistance of the metal substrate.

[0086] Micro-arc oxidation is a technology that directly grows a ceramic layer in situ on the metal surface. The film obtained by micro-arc oxidation not only has the advantages of strong adhesion and good corrosion resistance, but also can greatly improve the surface hardness, wear resistance, electrical insulation and other properties, which can play a good protective role on the substrate. The surface of the metal substrate after micro-arc oxidation will produce a porous structure. The preparation method of the present invention, for these porous structures, first uses a suspension of liquid metal to seal these porous structures. On the one hand, the sealing treatment can reduce the attachment of microorganisms in the holes; on the other hand, the sealing treatment can first fill the liquid metal into the porous structure. The liquid metal acts as an electron donor, and the metal ions in the subsequent metal salt solution act as electron acceptors. The large difference in standard reduction potential between the two makes the liquid metal and the metal ions in the metal salt solution undergo a spontaneous electrocouple replacement reaction, thereby forming polygonal particles and filling the porous structure.

[0087] In some embodiments of the present invention, the metal substrate comprises a titanium alloy.

[0088] 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 the corrosive environment of seawater and marine atmosphere, due to the high potential of titanium alloy, galvanic corrosion will occur when it is 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 alloy. However, the micro-arc oxidation coating is an arc discharge on the surface of the workpiece under high pressure. There are a large number of discharge channels in the obtained oxidation coating, resulting in a large number of micron-scale micropores in the micro-arc oxidation coating. In a corrosive environment, the presence of these micropores not only provides a channel for the corrosive medium to penetrate into the substrate, but also accelerates the speed of its erosion of the substrate. Therefore, it is necessary to further treat the oxidation coating to isolate the substrate from the contact with the external environment medium and increase its anti-corrosion performance. The present invention uses the spontaneous galvanic replacement reaction of liquid metal and metal salt solution on the surface of the metal substrate after micro-arc oxidation to form polygonal particles and fill the micropores, thereby obtaining a functional coating with good performance against biofouling.

[0089] In some embodiments of the present invention, the titanium alloy includes TC4, TA9, TA9-1 and TA10.

[0090] In some embodiments of the present invention, the titanium alloy is TC4.

[0091] In some embodiments of the present invention, the method for preparing the liquid metal suspension is: adding the liquid metal to an alcohol solution and performing ultrasonic treatment.

[0092] In some embodiments of the present invention, the liquid metal is gallium liquid metal.

[0093] In some embodiments of the present invention, the concentration of the liquid metal suspension is 0.2 mol / L to 0.5 mol / L.

[0094] In some embodiments of the present invention, the alcohol solution includes at least one of methanol, ethanol or ethylene glycol.

[0095] In some embodiments of the present invention, the alcohol solution is ethanol.

[0096] In some embodiments of the present invention, the ultrasonic treatment can be performed by an ultrasonic cell disruptor.

[0097] In some embodiments of the present invention, the ultrasonic treatment time is 0.1 h to 1 h.

[0098] In some embodiments of the present invention, the ultrasonic treatment time is 0.1 h to 0.5 h.

[0099] In some embodiments of the present invention, the ultrasonic treatment time may be 0.5 h.

[0100] In some embodiments of the present invention, the sealing treatment method is: applying liquid metal suspension droplets to the pre-treated surface of the metal substrate, and moving the entire sample into a vacuum container, leaving it to stand, and repeating the process multiple times.

[0101] In some embodiments of the present invention, the vacuum degree during the sealing process can be 5×10 -3 Pa.

[0102] In some embodiments of the present invention, during the sealing process, the standing time may be 5 minutes.

[0103] In some embodiments of the present invention, the number of repetitions may be 4 times.

[0104] It should be noted that the purpose of sealing treatment is to reduce the attachment of microorganisms in the holes.

[0105] In some embodiments of the present invention, the temperature of the dry oxidation is 40°C to 80°C.

[0106] In some embodiments of the present invention, the temperature of the dry oxidation is 40°C to 60°C.

[0107] In some embodiments of the present invention, the temperature of dry oxidation may be 60°C.

[0108] In some embodiments of the present invention, the drying and oxidation time is 3 hours to 5 hours.

[0109] In some embodiments of the present invention, the drying and oxidation time may be 4 hours.

[0110] 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.

[0111] In some embodiments of the present invention, the concentration of the metal salt solution is 0.1 mol / L to 1 mol / L.

[0112] In some embodiments of the present invention, the concentration of the metal salt solution is 0.1 mol / L to 0.5 mol / L.

[0113] In some embodiments of the present invention, the concentration of the metal salt solution may be about 0.1 mol / L.

[0114] In some embodiments of the present invention, the metal salt solution is a copper sulfate solution.

[0115] In some embodiments of the present invention, the reaction time is 0.1 h to 1 h.

[0116] In some embodiments of the present invention, the reaction time is 0.1 h to 0.5 h.

[0117] In some embodiments of the present invention, the reaction time may be about 0.5 h.

[0118] In some other embodiments of the present invention, the present invention provides the use of anti-biofouling functional coating in marine equipment.

[0119] It can be understood that the anti-biofouling functional coating of the present invention can exert a good antifouling effect when applied to marine equipment because copper and gallium ions can synergistically reduce the attachment rate of sulfate-reducing bacteria, and has unique antibacterial and non-toxic properties and is environmentally friendly.

[0120] In some embodiments of the present invention, marine equipment includes marine transportation equipment, marine scientific research equipment, marine development equipment and marine protection equipment.

[0121] Among them, marine transport 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; according to the navigation area, there are ocean-going ships, offshore ships, coastal ships and inland ships; according to the power plant, there are steam ships, internal combustion engine ships, steam turbine ships, electric ships and nuclear-powered ships; according to the propulsion method, there are paddle ships, propeller ships, flat-rotating propellers and sail-aided ships; according to the navigation method, there are self-propelled ships and non-self-propelled ships; according to the navigation state, 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., and has broad application prospects as a ship material. However, due to its good biocompatibility, titanium alloy has serious biological fouling problems. Most marine organisms, including microorganisms, can adhere and grow on the surface of titanium alloy materials, resulting in biological fouling, causing safety problems in long-term service, which seriously restricts the application of titanium alloy in the marine environment. When the coating of the present invention is applied to the surface of a titanium alloy material, it can prevent marine organisms from adhering and growing on the surface of the titanium alloy material, thereby preventing the occurrence of biological fouling.

[0122] Marine scientific research equipment mainly refers to various equipment specially used for scientific investigation and experimental activities of marine resources, environment, etc. Its main carriers are marine survey and marine scientific research ships, as well as various observation and detection equipment arranged on the shore, sea surface, underwater and seabed. When the coating of the present invention is used on the surface of marine scientific research equipment, it can prevent the adhesion and growth of marine organisms on the surface of titanium alloy materials, and prevent the occurrence of biological fouling.

[0123] Marine development equipment mainly refers to equipment used for the development of marine oil and gas resources, marine biological resources, marine new energy, deep-sea solid mineral resources, as well as new marine space resource utilization equipment and seawater resource comprehensive utilization equipment. When the coating of the present invention is used on the surface of marine development equipment, it can prevent the adhesion and growth of marine organisms on the surface of titanium alloy materials and prevent the occurrence of biological fouling.

[0124] Marine protection equipment mainly refers to marine monitoring ships, patrol ships, coast guard ships and other marine rights protection equipment, emergency rescue ships, salvage ships and other marine security equipment, as well as oil spill recovery ships, marine garbage recovery equipment and other marine environmental protection equipment. When the coating of the present invention is applied to the surface of marine protection equipment, it can also prevent the adhesion and growth of marine organisms on the surface of titanium alloy materials, thereby preventing the occurrence of biological fouling.

[0125] The technical solution of the present invention will be better understood with reference to specific embodiments below.

[0126] Example 1

[0127] This embodiment provides an anti-biofouling functional coating, in which a porous structure is distributed, and the porous structure is filled with polygonal particles, and the element composition of the polygonal particles includes Cu and Ga.

[0128] The specific preparation method comprises the following steps:

[0129] (1) The titanium alloy TC4 substrate was ground, polished, and cleaned in sequence to remove the oxide film and oil stains on its surface. The sample was then suspended in an electrolyte for micro-arc oxidation treatment to obtain a corrosion-resistant and porous titanium dioxide oxide layer (denoted as TC4-MAO).

[0130] The voltage of the micro-arc oxidation treatment is 260V, the duty cycle is 30%, the frequency is 300HZ, and the oxidation time is 15min.

[0131] (2) 0.4 g of gallium-based liquid metal was added to 15 mL of ethanol solution, and ultrasonically treated for 30 min under the action of an ultrasonic cell disruptor to obtain a suspension of gallium liquid metal particles with a diameter of about 400 nm.

[0132] (3) Take 200 μL of the gallium liquid metal particle suspension prepared in step (2) and drop it onto the surface of TC4-MAO prepared in step (1), and move the entire sample into a vacuum container with a vacuum degree of 5×10 -3 Pa, let stand for 5 minutes.

[0133] (4) Repeat step (3) 4 times, then rinse the gallium liquid metal particles remaining on the surface with ethanol, and dry and oxidize at 60° C. for 4 h to obtain a liquid metal-sealed titanium alloy coating (denoted as TC4-MAO-LM).

[0134] (5) The TC4-MAO-LM sample prepared in step (4) was immersed in 0.1 mol / L CuSO 4 The sample was placed in the solution for 30 min, and the surface was rinsed with deionized water and dried at 60 °C for 1 h to obtain an anti-biofouling functional coating (denoted as TC4-MAO-LMCu).

[0135] Comparative Example 1

[0136] This comparative example provides a functional coating.

[0137] The specific preparation method is:

[0138] The titanium alloy TC4 substrate was ground, polished and cleaned in sequence to remove the oxide film and oil stains on its surface, and then the sample was suspended in an electrolyte for micro-arc oxidation treatment to obtain a corrosion-resistant and porous titanium dioxide oxide layer (denoted as TC4-MAO).

[0139] The voltage of the micro-arc oxidation treatment is 260V, the duty cycle is 30%, the frequency is 300HZ, and the oxidation time is 15min.

[0140] Comparative Example 2

[0141] This comparative example provides a functional coating.

[0142] The specific preparation method is:

[0143] (1) The titanium alloy TC4 substrate was ground, polished, and cleaned in sequence to remove the oxide film and oil stains on its surface, and then the sample was suspended in an electrolyte for micro-arc oxidation treatment to obtain a corrosion-resistant and porous titanium dioxide oxide layer.

[0144] The voltage of the micro-arc oxidation treatment is 260V, the duty cycle is 30%, the frequency is 300HZ, and the oxidation time is 15min.

[0145] (2) 0.4 g of gallium-based liquid metal was added to 15 mL of ethanol solution, and ultrasonically treated for 30 min under the action of an ultrasonic cell disruptor to obtain a suspension of gallium liquid metal particles with a diameter of about 400 nm.

[0146] (3) Take 200 μL of the suspension prepared in step (2) and apply it dropwise to the surface of TC4-MAO prepared in step (1), and move the entire sample into a vacuum container with a vacuum degree of 5×10 -3 Pa, let stand for 5 minutes.

[0147] (4) Repeat step (3) 4 times, then rinse the gallium liquid metal particles remaining on the surface with ethanol, and dry and oxidize at 60° C. for 4 h to obtain a liquid metal-sealed titanium alloy coating (denoted as TC4-MAO-LM).

[0148] The above preparation process is as follows Figure 1 shown.

[0149] Performance Testing

[0150] Figure 2 This is a microscopic morphology of the coating surface prepared in Example 1.

[0151] from Figure 2 It can be seen that the anti-biofouling functional coating prepared in Example 1 has porous structures distributed therein, and these porous structures are filled with polygonal particles.

[0152] The coating prepared in Example 1 was characterized by X-ray powder diffraction. Figure 3 shown.

[0153] according to Figure 3 It can be seen that there are Ti and TiO in the coating. 2 ,Cu,Cu 2+1 O, Cu 9 Ga 4 The presence of five crystal structures indicates the presence of Cu and Ga in the coating. The components of the polygonal particles include Cu, Cu 2+1 O and Cu 9 Ga 4 .

[0154] Figure 4 The following are test graphs of the anti-sulfate-reducing bacteria adhesion performance of the untreated TC4 sample, the coatings prepared in Example 1 and Comparative Examples 1-2. Figure 4 It can be seen that after immersion in artificial seawater with sulfate-reducing bacteria for 14 days, the surface SRB attachment rates of untreated TC4 and TC4-MAO (Comparative Example 1) were 22.89% and 25.91%, respectively, and sulfate-reducing bacteria formed a dense biofilm on their surfaces.

[0155] However, the attachment rates of sulfate-reducing bacteria on the surfaces of the TC4-MAO-LM (Comparative Example 2) and TC4-MAO-LMCu (Example 1) coatings were only 0.89% and 0.02%, respectively, indicating that the TC4-MAO-LMCu coating of the present invention has good antibacterial properties.

[0156] It should be noted that, although the antifouling effect of the coating can also be evaluated by different microorganisms, those skilled in the art know that the attachment rate of sulfate-reducing bacteria is sufficient to illustrate the bio-antifouling performance of the coating.

[0157] The present invention also provides the application of the anti-biofouling functional coating in marine equipment.

[0158] It can be understood that the anti-biofouling functional coating of the present invention can exert a good antifouling effect when applied to marine equipment because copper and gallium ions can synergistically reduce the attachment rate of sulfate-reducing bacteria, and has unique antibacterial and non-toxic properties and is environmentally friendly.

[0159] In some embodiments of the present invention, marine equipment includes marine transportation equipment, marine scientific research equipment, marine development equipment and marine protection equipment.

[0160] The present invention has been described in detail above in conjunction with the embodiments, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge scope of ordinary technicians in the relevant technical field without departing from the purpose of the present invention.

Claims

1. A method for preparing an anti-biofouling functional coating, characterized in that: The preparation method comprises: sealing the surface of the pretreated metal substrate with a suspension of liquid metal, drying and oxidizing, and then reacting in a metal salt solution to form the anti-biofouling functional coating, wherein the liquid metal comprises at least one of gallium liquid metal, gallium indium liquid metal and gallium indium tin liquid metal, and the metal salt solution comprises at least one of copper sulfate solution, copper chloride solution, silver sulfate solution and silver chloride solution; A porous structure is distributed in the anti-biofouling functional coating, and polygonal particles are filled in the porous structure. The element composition of the polygonal particles includes Cu and Ga.

2. The preparation method according to claim 1, characterized in that: The pretreatment includes grinding, polishing, cleaning and oxidation treatment performed in sequence.

3. The preparation method according to claim 1, characterized in that: The preparation method of the liquid metal suspension is: adding the liquid metal into an alcohol solution and performing ultrasonic treatment.

4. The preparation method according to claim 1, characterized in that: The temperature of the drying oxidation is 40°C to 80°C.

5. The preparation method according to claim 1, characterized in that: The drying and oxidation time is 3h to 5h.

6. The preparation method according to claim 1, characterized in that: The concentration of the metal salt solution is 0.1 mol / L to 1 mol / L.

7. The preparation method according to claim 1, characterized in that: The reaction time is 0.1h to 1h.

8. The preparation method according to claim 1, characterized in that: The components of the polygonal particles include Cu, Cu 2+1 O and Cu9Ga4.

9. The preparation method according to claim 1, characterized in that: The thickness of the anti-biofouling functional coating is 5 μm to 10 μm.

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