A 4D multi-response super-lubricating and antifouling coating based on biomimetic cilia and its preparation method

Abstract

This invention discloses a method for preparing a 4D multi-response super-lubricating antifouling coating based on biomimetic cilia, comprising the following steps: (1) preparation of ZIF-8; (2) preparation of ZIF-8 loaded with photoresponsive NO release agent; 1-100 parts by weight of ZIF-8 and 1-100 parts by weight of photoresponsive NO release agent prepared in step (1) are dispersed in 100-1000 parts by weight of solvent α, stirred at room temperature for 1-4 hours, centrifuged to obtain a solid, washed with solvent α and centrifuged to obtain a solid, and freeze-dried to obtain ZIF-8 loaded with photoresponsive NO release agent. (3) preparation of antifouling coating. The antifouling coating of this invention utilizes the vibration of magnetic cilia under an applied alternating magnetic field, the barrier anti-adhesion effect of the surface lubricating layer, and the biocidal effect of NO released by photoresponsiveness, to coordinate in the 4D dimensions of space and time through a multi-response mechanism, effectively controlling the antifouling process in a multi-dimensional intelligent and precise manner, overcoming the problems of low antifouling dimension and insufficient antifouling precision of traditional coatings.

Description

Technical Field

[0001] This invention relates to marine antifouling coating technology, and in particular to a 4D multi-response super-lubricating antifouling coating based on biomimetic cilia and its preparation method. Background Technology

[0002] Underwater robots, unmanned submersibles, and marine buoy workstations, among other shallow-sea equipment, have shown enormous application potential in scientific research and economic fields. However, marine equipment operating in the marine environment is susceptible to fouling by marine organisms, significantly impacting human production and daily life and causing substantial economic losses. The simplest and most effective method to address marine biofouling is to apply marine antifouling coatings.

[0003] Since January 2008, the International Maritime Organization has banned the global use of tributyltin antifouling coatings, which are non-biodegradable and teratogenic, thus bringing widespread attention to environmentally friendly antifouling coatings. Slippery liquid-infused porous surfaces (SLIPS) have attracted continued attention due to their low surface energy, low Young's modulus, and dynamic lubrication. Traditional antifouling coatings typically operate on a two- or three-dimensional scale, limited to the 2D plane or 3D surface microstructure of the coating. However, marine biofouling is a four-dimensional process, involving multiple dimensions of time and space. Therefore, to prevent the attachment of marine fouling organisms, antifouling technology should also regulate the antifouling process from a 4D spatiotemporal perspective, requiring different response modes to adjust the antifouling mode as needed in time and space. Furthermore, traditional marine antifouling coatings only offer a single antifouling mode, failing to meet the needs of different occasions and times. Therefore, 4D multi-response antifouling coatings hold significant research potential. Summary of the Invention

[0004] This invention aims to address the problems of limited antifouling effect and low dimensionality of the antifouling process in traditional antifouling coatings. To overcome the shortcomings of existing technologies, this invention provides a 4D multi-response super-lubricating antifouling coating based on biomimetic cilia and its preparation method.

[0005] To solve the technical problem, the solution of the present invention includes the following steps:

[0006] Step (1) Preparation of ZIF-8:

[0007] Solution A: Dissolve 1-100 parts by weight of 2-methylimidazolium in 100-1000 parts by weight of solvent α.

[0008] Solution B: Dissolve 1-100 parts by weight of zinc salt in 100-1000 parts by weight of solvent α.

[0009] Solution B was added to solution A and stirred at 10-1000 rpm for 10-100 min. After centrifugation to obtain the solid, it was washed with solvent α and centrifuged again to obtain the solid, which was then freeze-dried to obtain ZIF-8.

[0010] Step (2) Preparation of ZIF-8 loaded with photoresponsive NO release agent:

[0011] 1-100 parts by weight of ZIF-8 and 1-100 parts by weight of the photoresponsive NO releaser prepared in step (1) were dispersed in 100-1000 parts by weight of solvent α. The mixture was stirred at room temperature for 1-4 hours, and after centrifugation to obtain a solid, it was washed with solvent α and centrifuged again to obtain a solid. ZIF-8 loaded with the photoresponsive NO releaser was obtained by freeze-drying.

[0012] Step (3) Preparation of antifouling coating:

[0013] In 1-100 parts by weight of Ecoflex TM Component A of commercial silicone and an equal weight of Ecoflex TM In the B component of commercial organosilicon, 1-100 parts by weight of ZIF-8 loaded with photoresponsive NO release agent prepared in step (2) above, 1-100 parts by weight of magnetic particles, 1-100 parts by weight of lubricating oil, 1-10 parts by weight of matching organosilicon curing accelerator, and 1-100 parts by weight of solvent β are added and dispersed evenly to obtain an antifouling coating.

[0014] Step (4) Painting and application method:

[0015] Clean the surface to be coated and uniformly apply the antifouling coating described in step (3) to the surface using air spraying. The wet film thickness is 500-5000 μm. Place a neodymium iron boron permanent magnet of the same size as the substrate directly below it at a distance of 0-10 cm. Under the magnetic field, the magnet self-assembles to form a cilia structure. After thorough drying under ventilated and dry conditions at room temperature, remove the permanent magnet to obtain a 4D multi-response super-lubricating antifouling coating based on biomimetic cilia.

[0016] Furthermore, when using this coating, a magnetic field with a continuously alternating magnetic field direction must be configured below or above the coating to drive the continuous magnetic response movement of the biomimetic cilia.

[0017] In this invention, the zinc salt refers to one of zinc nitrate hexahydrate or zinc acetate dihydrate.

[0018] In this invention, the photoresponsive NO release agent refers to N,N'-disec-butyl-N,N-dinitroso-1,4-phenylenediamine (BNN6).

[0019] In this invention, solvent α refers to one or more of water, methanol, ethanol, and N,N-dimethylformamide.

[0020] In this invention, solvent β refers to one or more of tetrahydrofuran, xylene, ethyl acetate, and n-hexane.

[0021] In this invention, the Ecoflex TM Commercially available silicone refers to Ecoflex, a product of SMOOTH-ON Inc. in the United States. TM 5. Ecoflex TM 00-50, Ecoflex TM 00-30, Ecoflex TM 00-33AF, Ecoflex TM 00-20, Ecoflex TM 00-20FAST and Ecoflex TM One of 00-10.

[0022] In this invention, the accompanying silicone curing accelerator refers to Plat-Cat, a product of SMOOTH-ON Inc., USA.

[0023] In this invention, the magnetic particles refer to one or more of carbonyl iron, iron(II,III) oxide, and cobalt particles with a particle size of 0.1-10 μm.

[0024] In this invention, the lubricating oil refers to one or more of dimethyl silicone oil, methyl fluorosilicone oil, and perfluoropolyether.

[0025] Description of the principle of this invention:

[0026] The formation of marine biofouling is a four-dimensional process, encompassing multiple dimensions of time and space. However, traditional antifouling coatings typically only offer two or three dimensions of protection, limited to the 2D plane or 3D surface microstructure of the coating. Therefore, to prevent the attachment of marine fouling organisms, antifouling technology should also regulate the antifouling process from a 4D spatiotemporal perspective, requiring different response mechanisms to adjust the antifouling mode as needed, both temporally and spatially.

[0027] like Figure 1As shown, this invention introduces magnetic and optical response mechanisms into the SLIPS super-lubricating coating, enabling 4D control of the coating's antifouling performance from both spatial and temporal perspectives. ① Spatial dimension (3D) control of magnetic response: Magnetic particles (carbonyl iron, iron(II,III) oxide, and cobalt) are introduced into the silicone polymer. Under the influence of a magnetic field, these particles can overcome gravity and form an ordered oriented structure along the magnetic field lines. During the coating drying process, a magnetic field formed by a neodymium iron boron permanent magnet is used to cause the magnetic fluid mixture of silicone polymer precursor, magnetic particles, and solvent to self-assemble into a Rosensweig cone-shaped three-dimensional structure under the combined action of magnetic force, surface tension, and gravity. After the silicone polymer cross-links and cures, and the solvent evaporates and dries, a SLIPS super-lubricating antifouling coating with biomimetic cilia is formed. During coating use, removing the neodymium iron boron permanent magnet requires the application of several continuous alternating magnetic fields. This causes the magnetic cilia to continuously bend and rotate under the influence of the constantly changing magnetic field force, preventing the adhesion of fouling microorganisms through the continuous movement of the cilia.

[0028] ② Temporal (1D) Regulation of Photoresponse: Nitric oxide (NO) is a highly efficient gaseous antibacterial agent that can generate oxidation / nitrosation products, damaging the cell membranes and organelles of contaminating microorganisms. NO is widely present in animals, thus exhibiting excellent biocompatibility. N,N'-di-sec-butyl-N,N-dinitroso-1,4-phenylenediamine (BNN6) is a highly efficient photoresponsive NO releaser; under ultraviolet light, each molecule of BNN6 degrades to generate two molecules of NO. Since sunlight contains ultraviolet wavelengths, BNN6 also exhibits excellent photoresponsive NO release performance in response to sunlight. As a common metal-organic framework, ZIF-8 possesses abundant porosity, stability, and a convenient synthesis method. This invention utilizes ZIF-8 as a carrier, loading BNN6 into its abundant pores. The synthesized composite particles are introduced into the coating blend, forming a biomimetic cilia-like 4D multi-responsive superlubricating antifouling coating during the aforementioned magnetic field self-assembly process. During the application of the coating, the release of the gaseous antibacterial agent NO is controlled by the presence or intensity of light at different times, thereby achieving the regulation of the coating's bactericidal and antifouling performance over time.

[0029] Compared with the prior art, the beneficial effects of this invention are:

[0030] 1. The antifouling coating of the present invention utilizes the vibration of magnetic cilia under an applied alternating magnetic field, the barrier anti-adhesion effect of the surface lubricating layer, and the biocidal effect of NO released in response to light. Through the synergistic effect of multiple response mechanisms in the 4D dimensions of space and time, it effectively achieves multi-dimensional intelligent and precise control of the antifouling process, overcoming the problems of low antifouling dimension and insufficient antifouling precision of traditional coatings.

[0031] 2. The antifouling coating of the present invention intelligently adjusts the strength of its antifouling performance based on magnetic / optical response. By adjusting the frequency of cilia movement under a magnetic field and the presence or absence of light, the antifouling performance of the coating is enhanced as needed, improving antifouling efficiency and reducing waste of antifouling agents. This overcomes the problems of uncontrollable antifouling agent release, uncontrollable antifouling performance intensity, and poor on-demand response adjustment performance of traditional antifouling coatings, effectively enhancing the intelligent antifouling application performance of light-transmitting parts of shallow sea equipment. Attached Figure Description

[0032] Figure 1 Mechanism of 4D multi-response super-lubricating antifouling coating based on biomimetic cilia.

[0033] Figure 2 Results of antibacterial performance tests on the coating. Detailed Implementation

[0034] The invention will be further described in detail below with reference to specific embodiments and comparative examples. These embodiments will enable those skilled in the art to more fully understand the invention, but are not intended to limit the invention in any way.

[0035] Example 1

[0036] The preparation and application method of a 4D multi-response super-lubricating and antifouling coating based on biomimetic cilia in this embodiment is as follows:

[0037] (1) Preparation of ZIF-8:

[0038] Solution A: Dissolve 1 part by weight of 2-methylimidazole in 100 parts by weight of water.

[0039] Solution B: Dissolve 1 part by weight of zinc nitrate hexahydrate in 100 parts by weight of water.

[0040] Add B to A and stir at 10 rpm for 10 min. After centrifugation to obtain the solid, wash with water and centrifuge again to obtain the solid. Freeze-dry to obtain ZIF-8.

[0041] (2) Preparation of ZIF-8 loaded with a photoresponsive NO release agent:

[0042] One part by weight of ZIF-8 and one part by weight of BNN6 prepared in (1) were dispersed in 100 parts by weight of water. After stirring at room temperature for 1 h, the solid was separated by centrifugation, washed with water and centrifuged again to obtain a solid. ZIF-8 loaded with photoresponsive NO release agent was obtained by freeze drying.

[0043] (3) Preparation of antifouling coatings:

[0044] In 1 part by weight of Ecoflex TM 5 parts of component A and an equal weight of Ecoflex TMIn component B of 5, 1 part by weight of ZIF-8, the photoresponsive NO release agent prepared in (2) above, 1 part by weight of carbonyl iron, 1 part by weight of dimethyl silicone oil, 1 part by weight of Plat-Cat, and 1 part by weight of tetrahydrofuran are added and dispersed evenly to obtain an antifouling coating.

[0045] (4) Painting and application methods:

[0046] Clean the surface to be sprayed, and uniformly apply the antifouling coating described in (3) to the surface by air spraying, with a wet film thickness of 500 μm. Place a neodymium iron boron permanent magnet of the same size as the substrate directly below it at a distance of 0 cm, and allow it to self-assemble into a cilia structure under a magnetic field. After thorough drying under ventilated and dry room temperature conditions, remove the permanent magnet to obtain a 4D multi-response super-lubricating antifouling coating based on biomimetic cilia. When using this coating, a continuously alternating magnetic field direction must be configured below or above the coating to drive the continuous magnetic response movement of the biomimetic cilia.

[0047] Example 2

[0048] The preparation and application method of a 4D multi-response super-lubricating and antifouling coating based on biomimetic cilia in this embodiment is as follows:

[0049] (1) Preparation of ZIF-8:

[0050] Solution A: Dissolve 20 parts by weight of 2-methylimidazole in 200 parts by weight of methanol.

[0051] Solution B: Dissolve 20 parts by weight of zinc nitrate hexahydrate in 2000 parts by weight of methanol.

[0052] Add B to A and stir at 200 rpm for 20 min. After centrifugation to obtain a solid, wash with methanol and centrifuge again to obtain a solid. Freeze-dry to obtain ZIF-8.

[0053] (2) Preparation of ZIF-8 loaded with a photoresponsive NO release agent:

[0054] 20 parts by weight of ZIF-8 and 20 parts by weight of BNN6 prepared in (1) were dispersed in 200 parts by weight of methanol. The mixture was stirred at room temperature for 1.5 h, and after centrifugation, the solid was washed with methanol and centrifuged again. ZIF-8 loaded with photoresponsive NO release agent was obtained by freeze drying.

[0055] (3) Preparation of antifouling coatings:

[0056] In 20 parts by weight of Ecoflex TM 00-50 of component A and an equal weight of Ecoflex TMIn component B of 00-50, 20 parts by weight of ZIF-8, the photoresponsive NO release agent prepared in (2) above, 20 parts by weight of carbonyl iron, 20 parts by weight of dimethyl silicone oil, 2 parts by weight of Plat-Cat, and 20 parts by weight of xylene are added and dispersed evenly to obtain an antifouling coating.

[0057] (4) Painting and application methods:

[0058] Clean the surface to be sprayed, and uniformly apply the antifouling coating described in (3) to the surface by air spraying, with a wet film thickness of 1000 μm. Place a neodymium iron boron permanent magnet of the same size as the substrate directly below it at a distance of 2 cm, and allow it to self-assemble into a cilia structure under a magnetic field. After thorough drying under ventilated and dry room temperature conditions, remove the permanent magnet to obtain a 4D multi-response super-lubricating antifouling coating based on biomimetic cilia. When using this coating, a continuously alternating magnetic field direction must be configured below or above the coating to drive the continuous magnetic response movement of the biomimetic cilia.

[0059] Example 3

[0060] The preparation and application method of a 4D multi-response super-lubricating and antifouling coating based on biomimetic cilia in this embodiment is as follows:

[0061] (1) Preparation of ZIF-8:

[0062] Solution A: Dissolve 40 parts by weight of 2-methylimidazole in 400 parts by weight of ethanol.

[0063] Solution B: Dissolve 40 parts by weight of zinc nitrate hexahydrate in 100-1000 parts by weight of ethanol.

[0064] Add B to A and stir at 400 rpm for 40 min. After centrifugation to obtain the solid, wash with ethanol and centrifuge again to obtain the solid. Freeze-dry to obtain ZIF-8.

[0065] (2) Preparation of ZIF-8 loaded with a photoresponsive NO release agent:

[0066] 40 parts by weight of ZIF-8 and 40 parts by weight of BNN6 prepared in (1) were dispersed in 400 parts by weight of ethanol. After stirring at room temperature for 2 h, the solid was separated by centrifugation, washed with ethanol and centrifuged again. ZIF-8 loaded with photoresponsive NO release agent was obtained by freeze drying.

[0067] (3) Preparation of antifouling coatings:

[0068] In 40 parts by weight of Ecoflex TM Component A of 00-30 and an equal weight of Ecoflex TMIn component B of 00-30, 40 parts by weight of ZIF-8, the above-prepared (2) loaded with photoresponsive NO release agent, 40 parts by weight of iron(III) oxide, 40 parts by weight of methyl fluorosilicone oil, 4 parts by weight of Plat-Cat, and 40 parts by weight of ethyl acetate were added and dispersed evenly to obtain an antifouling coating.

[0069] (4) Painting and application methods:

[0070] Clean the surface to be coated and uniformly apply the antifouling coating described in (3) to the surface by air spraying. The wet film coating thickness is 2000 μm. Place a neodymium iron boron permanent magnet of the same size as the substrate at a distance of 4 cm directly below the substrate. Under the magnetic field, the magnet self-assembles to form a cilia structure. After drying fully under ventilated and dry room temperature conditions, remove the permanent magnet to obtain a 4D multi-response super-lubricating antifouling coating based on biomimetic cilia. When using this coating, a continuously alternating magnetic field direction must be configured below or above the coating to drive the continuous magnetic response movement of the biomimetic cilia.

[0071] Example 4

[0072] The preparation and application method of a 4D multi-response super-lubricating and antifouling coating based on biomimetic cilia in this embodiment is as follows:

[0073] (1) Preparation of ZIF-8:

[0074] Solution A: Dissolve 60 parts by weight of 2-methylimidazole in 600 parts by weight of N,N-dimethylformamide.

[0075] Solution B: Dissolve 60 parts by weight of zinc acetate dihydrate in 600 parts by weight of N,N-dimethylformamide.

[0076] Add B to A and stir at 600 rpm for 60 min. After centrifugation to obtain a solid, wash with N,N-dimethylformamide and centrifuge again to obtain a solid. Freeze-dry to obtain ZIF-8.

[0077] (2) Preparation of ZIF-8 loaded with a photoresponsive NO release agent:

[0078] 60 parts by weight of ZIF-8 and 60 parts by weight of BNN6 prepared in (1) were dispersed in 600 parts by weight of N,N-dimethylformamide. After stirring at room temperature for 3 h, the solid was obtained by centrifugation, washed with N,N-dimethylformamide and centrifuged again. ZIF-8 loaded with photoresponsive NO release agent was obtained by freeze drying.

[0079] (3) Preparation of antifouling coatings:

[0080] In 60 parts by weight of Ecoflex TMComponent A of 00-20 and an equal weight of Ecoflex TM In component B of 00-20, 60 parts by weight of ZIF-8, the photoresponsive NO release agent prepared in (2) above, 60 parts by weight of iron(III) oxide, 60 parts by weight of methyl fluorosilicone oil, 6 parts by weight of Plat-Cat, and 60 parts by weight of n-hexane were added and dispersed evenly to obtain an antifouling coating.

[0081] (4) Painting and application methods:

[0082] Clean the surface to be sprayed, and uniformly apply the antifouling coating described in (3) to the surface by air spraying, with a wet film thickness of 3000 μm. Place a neodymium iron boron permanent magnet of the same size as the substrate directly below it at a distance of 6 cm, and allow it to self-assemble into a cilia structure under a magnetic field. After thorough drying under ventilated and dry room temperature conditions, remove the permanent magnet to obtain a 4D multi-response super-lubricating antifouling coating based on biomimetic cilia. When using this coating, a continuously alternating magnetic field direction must be configured below or above the coating to drive the continuous magnetic response movement of the biomimetic cilia.

[0083] Example 5

[0084] The preparation and application method of a 4D multi-response super-lubricating and antifouling coating based on biomimetic cilia in this embodiment is as follows:

[0085] (1) Preparation of ZIF-8:

[0086] Solution A: Dissolve 80 parts by weight of 2-methylimidazole in 800 parts by weight of methanol.

[0087] Solution B: Dissolve 80 parts by weight of zinc acetate dihydrate in 800 parts by weight of methanol.

[0088] Add B to A and stir at 800 rpm for 80 min. After centrifugation to obtain a solid, wash with methanol and centrifuge again to obtain a solid. Freeze-dry to obtain ZIF-8.

[0089] (2) Preparation of ZIF-8 loaded with a photoresponsive NO release agent:

[0090] 80 parts by weight of ZIF-8 and 80 parts by weight of BNN6 prepared in (1) were dispersed in 800 parts by weight of methanol. The mixture was stirred at room temperature for 3.5 h, and after centrifugation, the solid was washed with methanol and centrifuged again. ZIF-8 loaded with photoresponsive NO release agent was obtained by freeze drying.

[0091] (3) Preparation of antifouling coatings:

[0092] In 80 parts by weight of Ecoflex TM00-33AF commercial silicone component A and an equal weight of Ecoflex TM In component B of 00-33AF, 80 parts by weight of ZIF-8 loaded with photoresponsive NO release agent prepared in (2) above, 80 parts by weight of cobalt particles, 80 parts by weight of perfluoropolyether, 8 parts by weight of Plat-Cat, and 80 parts by weight of xylene are added and dispersed evenly to obtain an antifouling coating.

[0093] (4) Painting and application methods:

[0094] Clean the surface to be sprayed, and uniformly apply the antifouling coating described in (3) to the surface by air spraying, with a wet film thickness of 4000 μm. Place a neodymium iron boron permanent magnet of the same size as the substrate at a distance of 8 cm directly below the substrate, and allow it to self-assemble into a cilia structure under a magnetic field. After thorough drying under ventilated and dry room temperature conditions, remove the permanent magnet to obtain a 4D multi-response super-lubricating antifouling coating based on biomimetic cilia. When using this coating, a continuously alternating magnetic field direction must be configured below or above the coating to drive the continuous magnetic response movement of the biomimetic cilia.

[0095] Example 6

[0096] The preparation and application method of a 4D multi-response super-lubricating and antifouling coating based on biomimetic cilia in this embodiment is as follows:

[0097] (1) Preparation of ZIF-8:

[0098] Solution A: Dissolve 100 parts by weight of 2-methylimidazole in 1000 parts by weight of solvent α.

[0099] Solution B: Dissolve 100 parts by weight of zinc acetate dihydrate in 1000 parts by weight of solvent α.

[0100] Add B to A and stir at 1000 rpm for 100 min. After centrifugation to obtain a solid, wash with ethanol and centrifuge again to obtain a solid. Freeze-dry to obtain ZIF-8.

[0101] (2) Preparation of ZIF-8 loaded with a photoresponsive NO release agent:

[0102] 100 parts by weight of ZIF-8 and 100 parts by weight of BNN6 prepared in (1) were dispersed in 1000 parts by weight of ethanol. After stirring at room temperature for 4 h, the solid was separated by centrifugation, washed with ethanol and centrifuged again to obtain a solid. ZIF-8 loaded with photoresponsive NO release agent was obtained by freeze drying.

[0103] (3) Preparation of antifouling coatings:

[0104] In 100 parts by weight of Ecoflex TM00-10 of component A and an equal weight of Ecoflex TM In component B of 00-10, 100 parts by weight of ZIF-8 loaded with photoresponsive NO release agent prepared in (2) above, 100 parts by weight of cobalt particles, 100 parts by weight of perfluoropolyether, 10 parts by weight of Plat-Cat, and 100 parts by weight of ethyl acetate are added and dispersed evenly to obtain an antifouling coating.

[0105] (4) Painting and application methods:

[0106] Clean the surface to be sprayed, and uniformly apply the antifouling coating described in (3) to the surface by air spraying, with a wet film thickness of 5000 μm. Place a neodymium iron boron permanent magnet of the same size as the substrate at a distance of 10 cm directly below the substrate, and allow it to self-assemble into a cilia structure under a magnetic field. After thorough drying under ventilated and dry room temperature conditions, remove the permanent magnet to obtain a 4D multi-response super-lubricating antifouling coating based on biomimetic cilia. When using this coating, a continuously alternating magnetic field direction must be configured below or above the coating to drive the continuous magnetic response movement of the biomimetic cilia.

[0107] Performance evaluation results:

[0108] (1) Antibacterial and antifouling properties

[0109] The test method was conducted in accordance with the national standard GB / T 21866-2008 "Determination of antibacterial properties and antibacterial effects of antibacterial coatings (films)".

[0110] Grade I: Antibacterial rate greater than 99.00%;

[0111] Grade II: Antibacterial rate greater than 90.00%.

[0112] Antibacterial properties are shown in Table 1 and Figure 2 .

[0113] (2) NO release performance

[0114] The average daily release rate of the coating in water was tested over 7 days under both sunlight and darkness conditions, with an immersion depth of 0.5 m. The concentration of released NO was detected using a Griess kit and a UV spectrophotometer.

[0115] The results of the release performance test are shown in Table 1.

[0116] Table 1. Experimental results of 4D multi-response super-lubricating antifouling coating based on biomimetic cilia.

[0117]

[0118] Note: The comparison is based on Ecoflex. TMThe silicones in the series are used as is, with equal amounts of components A and B mixed together, without adding other components, and the coating is applied and used in the same manner as in the examples.

[0119] This invention has been described in detail and specific embodiments have been illustrated by way of example in the Embodiments section. However, various modifications and alternatives can be made to this invention. It should be understood that this invention is not limited to the specific forms disclosed. This invention covers all modifications, equivalents, and alternatives that fall within the spirit and scope of the invention as defined by the appended claims.

Claims

1. A method for applying a 4D multi-responsive super-lubricating and anti-fouling coating based on biomimetic cilia, characterized in that, The preparation method of antifouling coating includes the following steps: (1) Preparation of ZIF-8; (2) Preparation of ZIF-8 loaded with a photoresponsive NO release agent: Disperse 1-100 parts by weight of ZIF-8 and 1-100 parts by weight of photoresponsive NO release agent prepared in step (1) in 100-1000 parts by weight of solvent α, stir at room temperature for 1-4 hours, centrifuge to obtain solid, wash with solvent α and centrifuge to obtain solid, freeze dry to obtain ZIF-8 loaded with photoresponsive NO release agent. (3) Preparation of antifouling coatings: In 1-100 parts by weight of Ecoflex™ commercial silicone A component and Ecoflex™ commercial silicone B component of equal weight to component A, 1-100 parts by weight of ZIF-8 loaded with photoresponsive NO release agent prepared in step (2), 1-100 parts by weight of magnetic particles, 1-100 parts by weight of lubricating oil, 1-10 parts by weight of matching silicone curing accelerator, and 1-100 parts by weight of solvent β are added and dispersed evenly to obtain an antifouling coating. The coating process is as follows: Clean the surface to be sprayed, and apply the prepared antifouling coating evenly to the surface by air spraying. The wet film coating thickness is 500-5000 μm. Place a neodymium iron boron permanent magnet of the same size as the substrate at a distance of 0-10 cm directly below the substrate. Under the magnetic field, the magnet self-assembles to form a cilia structure. After drying fully under ventilated and dry room temperature conditions, remove the permanent magnet to obtain a 4D multi-response super-lubricating antifouling coating based on biomimetic cilia.

2. The method of using a 4D multi-response super-lubricating and anti-fouling coating based on biomimetic cilia according to claim 1, characterized in that, When using the coating, a magnetic field with a continuously alternating direction must be configured below or above the coating to drive the continuous magnetic response movement of the biomimetic cilia.

3. The method of using a 4D multi-response super-lubricating and antifouling coating based on biomimetic cilia according to claim 1, characterized in that... Step (1) is implemented as follows: Solution A: Dissolve 1-100 parts by weight of 2-methylimidazolium in 100-1000 parts by weight of solvent α; Solution B: Dissolve 1-100 parts by weight of zinc salt in 100-1000 parts by weight of solvent α; Add B to A and stir at 10-1000 rpm for 10-100 min; after centrifugation to obtain the solid, wash with solvent α and centrifuge again to obtain the solid; freeze-dry to obtain ZIF-8.

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