Bionic physical dynamic surface antifouling material as well as preparation method and application thereof

Abstract

The invention discloses a bionic physical dynamic surface antifouling material as well as a preparation method and application thereof. According to the bionic physical dynamic surface anti-fouling material, a water-driven physical structure with a bionic whisker array is constructed through high-precision laser etching, a copper-tannic acid coordination network is constructed on the surfaces of whiskers through modification with a two-step method, and a double-synergistic anti-fouling mechanism of dynamic physical sweeping and static chemical sterilization is formed. Wherein the flexible bionic whisker structure endows the surface with efficient fouling desorption performance under the action of water flow, and the copper-tannic acid coordination network provides an excellent static contact sterilization function for the whisker. The preparation method is flexible and mild in condition, the antifouling surface of the obtained bionic physical dynamic surface antifouling material has high dynamic algae removal rate and high static bactericidal property, and the bionic physical dynamic surface antifouling material has application prospects in the field of marine antifouling.

Description

Technical Field

[0001] This invention belongs to the field of marine antifouling materials technology, specifically relating to a biomimetic physical dynamic surface antifouling material and its preparation method and application. Background Technology

[0002] Developing and utilizing marine resources has become a core path to achieving the "maritime power" strategy. However, the widespread problem of biofouling in the marine environment severely restricts the operational efficiency and service life of marine equipment. Marine biofouling refers to the biofouling formed by the adsorption, growth, and reproduction of microorganisms, plants, and animals on the surfaces of underwater facilities such as ship hulls, pipes, and sensors. It leads to increased ship drag, higher energy consumption, blockage of cooling water pipes and aquaculture cages, and induces equipment corrosion, causing significant economic losses. Antifouling coatings are currently the most mainstream antifouling technology. Among them, self-polishing or biodegradable coatings undergo chemical dissolution or hydrolysis under the action of seawater, continuously renewing the surface and releasing antifouling agents, and are known as "chemically dynamic surfaces." However, this type of technology relies on the continuous leaching of antifouling agents, posing potential ecological and environmental risks, and its service life is limited by the release rate of the antifouling agents.

[0003] In recent years, environmentally friendly "physically dynamic surfaces" have attracted widespread attention. These materials desorb fouling organisms through their inherent physical properties (such as elastic deformation) under the scouring effect of water flow. Furthermore, through biomimetic design (such as mimicking the structure of coral tentacles), surfaces with specific microstructures can be fabricated, generating synergistic ripples driven by water flow, significantly improving fouling removal efficiency at high flow rates. However, the cleaning efficiency of these structures is highly dependent on the external flow field; under low flow rates or still water conditions, their antifouling performance drops sharply due to a lack of sufficient driving kinetic energy. Therefore, endowing physically dynamic surfaces with static, active antifouling capabilities to compensate for their performance shortcomings at low flow rates is key to improving the overall antifouling performance of these materials and promoting their practical application. Summary of the Invention

[0004] To overcome the limitations of existing coral-tentacle-like structures in terms of insufficient static antifouling capability and limited overall antifouling performance under low flow rates, the primary objective of this invention is to provide a method for preparing a biomimetic physically dynamic surface antifouling material. This method, based on laser etching and a copper-tannic acid coordination network, is simple to operate, operates under mild conditions, and is low in cost, making it suitable for constructing large-area, high-efficiency antifouling materials. The high-precision laser etching technology used in preparing this antifouling coating enables large-area, controllable preparation of the biomimetic tentacle array mold. The silicone resin used in the molding process has a low elastic modulus and high replication accuracy, allowing the cured biomimetic tentacles to undergo significant synergistic deformation under water flow, thereby physically removing attached contaminants. Furthermore, by sequentially immersing the biomimetic tentacle surface in a tannic acid / silane coupling agent solution and a copper ion solution in a two-step process, a uniform and robust copper-tannic acid coordination network can be constructed on the surface of the biomimetic tentacle. This network is independent of water flow and can achieve sterilization through copper ions, thus significantly enhancing the antifouling capability of the physically dynamic surface under static or low flow rate conditions.

[0005] The second objective of this invention is to provide a biomimetic physical dynamic surface antifouling material prepared by the above-described preparation method.

[0006] A third objective of this invention is to provide applications of the aforementioned biomimetic physical dynamic surface antifouling material.

[0007] The primary objective of this invention is achieved through the following approach: A method for preparing a biomimetic physical dynamic surface antifouling material includes the following steps: (1) Preparation of biomimetic tentacle mold: Using laser etching technology, a negative mold of biomimetic tentacle array is processed on a substrate, namely biomimetic tentacle mold; the structural parameters of the biomimetic tentacle are: diameter 50~200 μm, length 100~300 μm, and center spacing is 2~10 times the diameter. (2) Preparation of silicone rubber surface by molding: The double-hydroxyl-terminated polydimethylsiloxane, crosslinking agent and catalyst are mixed in a mass ratio of 100:(1~10):(0.5~2), stirred thoroughly and degassed under vacuum, and then poured into the biomimetic tendril mold obtained in step (1), cured at room temperature and demolded to obtain a silicone rubber surface with a biomimetic tendril structure. (3) Activation treatment of silicone rubber surface: The silicone rubber surface with biomimetic tendril structure obtained in step (2) is subjected to air plasma treatment to obtain activated silicone rubber surface with biomimetic tendril structure. (4) Construction of tannic acid-silane pre-coating: The silicone rubber surface of the biomimetic tendril structure activated in step (3) was immersed in a Tris-HCl buffer solution of tannic acid and γ-aminopropyltriethoxysilane, gently shaken at room temperature, removed after immersion, rinsed with deionized water and dried to construct a tannic acid-silane pre-coating with biomimetic tendril structure. (5) Construction of copper-tannic acid coordination network: The biomimetic tendril structure with tannic acid-silane pre-coating obtained in step (4) is immersed in copper salt solution, taken out, rinsed with deionized water and dried to form a copper-tannic acid coordination network on the surface of the biomimetic tendril, and a biomimetic physical dynamic surface antifouling material is prepared.

[0008] Preferably, the substrate in step (1) is one of stainless steel plate, aluminum plate or silicon wafer.

[0009] Preferably, the power of the laser etching in step (1) is 20-200 W, the scanning speed is 200-500 mm / s, and the number of repeated scans is 1-6.

[0010] Preferably, the molecular weight of the hydroxyl-terminated polydimethylsiloxane in step (2) is 26,000 to 30,000 g / mol; the crosslinking agent is polyethyl silicate; and the catalyst is one of dibutyltin dilaurate, stannous octoate, dibutyltin diacetate, tetraisopropyl titanate, or tetrabutyl titanate.

[0011] Preferably, the room temperature curing time in step (2) is 12 to 24 hours.

[0012] Preferably, the cavity pressure of the air plasma treatment in step (3) is 300~500 Pa, the power of the air plasma treatment is 100-400 W, and the time of the air plasma treatment is 300~600 seconds.

[0013] Preferably, the Tris-HCl buffer solution of tannic acid and γ-aminopropyltriethoxysilane in step (4) is prepared by first pre-dissolving γ-aminopropyltriethoxysilane in anhydrous ethanol, and then dissolving tannic acid in Tris-HCl buffer solution to adjust the pH to 7-10; the concentration of the Tris-HCl buffer solution is 10~50 mM; the mass concentration of tannic acid is 0.5~20 mg / mL; and the mass ratio of γ-aminopropyltriethoxysilane to tannic acid is (0.2~5):1.

[0014] Preferably, the soaking time in step (4) is 6 to 24 hours.

[0015] Preferably, the copper salt solution in step (5) is any one of copper sulfate, copper chloride, and copper nitrate solutions; the copper ions (Cu) in the copper salt solution... 2+ The concentration of the ) is 1~20 mg / mL. Preferably, the soaking time in step (5) is 1~4 hours.

[0016] The second objective of this invention can be achieved through the following technical solutions: A biomimetic physical dynamic surface antifouling material is prepared by the above-mentioned preparation method.

[0017] Preferably, the biomimetic physical dynamic surface antifouling material has an elastic modulus of 0.3~1.5 MPa, a water contact angle of 55~75°, and a 24-hour antibacterial rate of not less than 90% against Pseudomonas aeruginosa.

[0018] The third objective of this invention can be achieved through the following technical solutions: An application of a biomimetic physical dynamic surface antifouling material in the field of marine antifouling, specifically, the application of the biomimetic physical dynamic surface antifouling material to ship hulls, marine platform structures, underwater sensors, aquaculture cages, or seawater pipeline systems.

[0019] The working principle of this invention is as follows: The biomimetic physical dynamic surface antifouling material of this invention achieves efficient and comprehensive antifouling through a synergistic mechanism of "physical dynamic cleaning" and "chemical static antifouling." Its working principle is as follows: First, a high aspect ratio biomimetic tentacle structure is constructed on the silicone rubber surface using high-precision laser etching and molding technology. This structure can generate significant coordinated oscillations under external water flow, physically removing macroscopic biofouling from marine organisms. Second, through a simple two-step surface modification method, a robust copper-tannic acid coordination network is constructed on the tentacle surface. This network, under static conditions independent of water flow, can effectively kill or inhibit microorganisms (such as bacteria and algal spores) through copper ions, preventing biofilm formation and initial attachment at the source, thus compensating for the performance shortcomings of water-driven purely physical dynamic surfaces in low flow rates or quiescent periods. This dual physical and chemical synergistic mechanism enables the surface to maintain excellent comprehensive antifouling performance under a wide range of conditions, from still water to flowing water.

[0020] Compared with the prior art, the present invention has the following advantages and beneficial effects: (1) Traditional water-driven physical dynamic surfaces rely heavily on external water flow to provide driving energy. Their cleaning ability drops sharply under low flow rate or still water conditions, resulting in the successful attachment of fouling organisms during the static window period. This invention introduces a copper-tannic acid coordination network to endow the surface with active, flow rate-independent chemical sterilization ability, realizing the effective synergy between dynamic physical cleaning and static chemical protection, and significantly broadening the effective antifouling working conditions. (2) The surface modification method described in this invention is mild and achieves functional modification through simple solution immersion. This process does not sacrifice the bulk mechanical properties of the silicone resin, thereby ensuring the stability of the biomimetic tentacles' physical dynamic cleaning ability. (3) The preparation method described in this invention uses a silane coupling agent to chemically bond the physical structure and the chemical functional layer into one, resulting in a strong chemical bond and avoiding the problem of functional layer detachment. (4) The preparation method described in this invention combines high-precision laser etching with a mild solution immersion method. The process is simple, the conditions are mild, and the cost is low. Furthermore, laser etching technology is easy to achieve large-area, high-consistency mold processing and has good prospects for large-scale production.

[0021] Instruction manual illustrations Figure 1 The diagram below illustrates the principle of the biomimetic dynamic surface antifouling material described in Example 1, where (a) shows the antifouling principle of the biomimetic dynamic surface antifouling material in a low flow rate environment, and (b) shows the antifouling principle of the biomimetic dynamic surface antifouling material in a high flow rate environment. Figure 2 The images are scanning electron microscope images of the biomimetic physical dynamic surface antifouling material described in Example 1, where (a) is a top view and (b) is a 45° tilted image; Figure 3 The contact angle measurement results are shown for the biomimetic dynamic surface antifouling material described in Example 1 and the sample of Comparative Example 1, where (a) is the contact angle image of the biomimetic dynamic surface antifouling material described in Example 1 and (b) is the contact angle image of the sample described in Comparative Example 1. Figure 4 This is a comparison of the bactericidal effects of the biomimetic dynamic surface antifouling material described in Example 1 and the sample of Comparative Example 1 against Pseudomonas aeruginosa. In the figure, (a) shows the bactericidal effect of the biomimetic dynamic surface antifouling material described in Example 1, and (b) shows the bactericidal effect of the sample described in Comparative Example 1. Detailed Implementation

[0022] The present invention will be further described in detail below with reference to specific embodiments, but the implementation of the present invention is not limited thereto. All materials used in the examples of the present invention are commercially available.

[0023] Example 1 The preparation method of the biomimetic physical dynamic surface antifouling material described in this embodiment includes the following steps: (1) Preparation of biomimetic tentacle mold: A negative mold of biomimetic tentacle array is processed on a substrate using laser etching technology, i.e., biomimetic tentacle mold; the specific parameters are: laser power 30 W, scanning speed 500 mm / s, repeated scanning 4 times; the structural parameters of the biomimetic tentacle are: diameter 50 μm, length 300 μm, center spacing 200 μm; (2) Preparation of silicone rubber surface by molding: 100 g of hydroxyl-terminated polydimethylsiloxane with a molecular weight of 28000 g / mol, 5 g of polyethyl silicate and 2 g of dibutyltin dilaurate are mixed, stirred thoroughly and degassed under vacuum, and then poured into the biomimetic tendon mold obtained in step (1). The mixture is cured for 24 hours at 25°C and 80% relative humidity. The silicone rubber surface with biomimetic tendon structure is obtained by demolding. (3) Activation treatment of silicone rubber surface: The silicone rubber surface with biomimetic tendril structure obtained in step (2) is subjected to air plasma treatment with a cavity pressure of 400 Pa and an air atmosphere treatment of 300 s to obtain the activated silicone rubber surface with biomimetic tendril structure. (4) Construction of tannic acid-silane pre-coating: 1.0 g of γ-aminopropyltriethoxysilane was pre-dissolved in 20 mL of anhydrous ethanol. 1.0 g of tannic acid was weighed and dissolved in 100 mL of Tris-HCl buffer (10 mM). The pre-dissolved components were then added and magnetically stirred until completely dissolved. The silicone rubber surface with the biomimetic tendril structure activated in step (3) was immersed in the Tris-HCl buffer of tannic acid and γ-aminopropyltriethoxysilane. The pH was adjusted to 8.5 with sodium hydroxide and gently shaken at room temperature for 24 hours. After immersion, the surface was removed, rinsed with deionized water, and dried to construct a tannic acid-silane pre-coating with a biomimetic tendril structure. (5) Construction of copper-tannic acid coordination network: The biomimetic tendril structure with tannic acid-silane pre-coating obtained in step (4) was immersed in copper ions (Cu) 2+ The solution was prepared by gentle shaking at room temperature for 2 hours in a CuSO4·5H2O solution with a concentration of 5 mg / mL. After removal, it was rinsed with deionized water and dried to form a copper-tannic acid coordination network on the surface of the biomimetic tentacles, which is the biomimetic physical dynamic surface antifouling material.

[0024] The antifouling principle diagram of the biomimetic dynamic surface antifouling material described in this embodiment is as follows: Figure 1 As shown. The scanning electron microscope results of the biomimetic physical dynamic surface antifouling material described in this embodiment are as follows. Figure 2 As shown. The contact angle results of the biomimetic physical dynamic surface antifouling material described in this embodiment are as follows. Figure 3 As shown in (a), the sterilization (Pseudomonas aeruginosa) effect of the biomimetic physical dynamic surface antifouling material described in this embodiment is illustrated in the photograph. Figure 4 As shown in (a).

[0025] Example 2 The preparation method of the biomimetic physical dynamic surface antifouling material described in this embodiment includes the following steps: (1) Preparation of biomimetic tentacle mold: A negative mold of biomimetic tentacle array is fabricated on a substrate using laser etching technology, i.e., biomimetic tentacle mold; the specific parameters are: laser power 30 W, scanning speed 500 mm / s, repeated scanning 4 times; the structural parameters of the biomimetic tentacle are: diameter 100 μm, length 300 μm, center spacing 200 μm; (2) Preparation of silicone rubber surface by molding: 100 g of hydroxyl-terminated polydimethylsiloxane with a molecular weight of 28000 g / mol, 5 g of polyethyl silicate and 2 g of dibutyltin dilaurate are mixed, stirred thoroughly and degassed under vacuum, and then poured into the biomimetic tendon mold obtained in step (1). The mixture is cured for 24 hours at 25°C and 80% relative humidity. The silicone rubber surface with biomimetic tendon structure is obtained by demolding. (3) Activation treatment of silicone rubber surface: The silicone rubber surface with biomimetic tendril structure obtained in step (2) is subjected to air plasma treatment with a cavity pressure of 400 Pa and an air atmosphere treatment of 300 s to obtain the activated silicone rubber surface with biomimetic tendril structure. (4) Construction of tannic acid-silane pre-coating: 1.0 g of γ-aminopropyltriethoxysilane was pre-dissolved in 20 mL of anhydrous ethanol. 1.0 g of tannic acid was weighed and dissolved in 100 mL of Tris-HCl buffer (10 mM). The pre-dissolved components were then added and magnetically stirred until completely dissolved. The silicone rubber surface with the biomimetic tendril structure activated in step (3) was immersed in the Tris-HCl buffer of tannic acid and γ-aminopropyltriethoxysilane. The pH was adjusted to 8.5 with sodium hydroxide and gently shaken at room temperature for 24 hours. After immersion, the surface was removed, rinsed with deionized water, and dried to construct a tannic acid-silane pre-coating with a biomimetic tendril structure. (5) Construction of copper-tannic acid coordination network: The biomimetic tendril structure with tannic acid-silane pre-coating obtained in step (4) was immersed in copper ions (Cu) 2+ The solution was prepared by gentle shaking at room temperature for 2 hours in a CuSO4·5H2O solution with a concentration of 5 mg / mL. After removal, it was rinsed with deionized water and dried to form a copper-tannic acid coordination network on the surface of the biomimetic tentacles, which is the biomimetic physical dynamic surface antifouling material.

[0026] Example 3 The preparation method of the biomimetic physical dynamic surface antifouling material described in this embodiment includes the following steps: (1) Preparation of biomimetic tentacle mold: A negative mold of biomimetic tentacle array is fabricated on a substrate using laser etching technology, i.e., biomimetic tentacle mold; the specific parameters are: laser power 30 W, scanning speed 500 mm / s, repeated scanning 4 times; the structural parameters of the biomimetic tentacle are: diameter 200 μm, length 300 μm, center spacing 200 μm; (2) Preparation of silicone rubber surface by molding: 100 g of hydroxyl-terminated polydimethylsiloxane with a molecular weight of 28000 g / mol, 5 g of polyethyl silicate and 2 g of dibutyltin dilaurate are mixed, stirred thoroughly and degassed under vacuum, and then poured into the biomimetic tendon mold obtained in step (1). The mixture is cured for 24 hours at 25°C and 80% relative humidity. The silicone rubber surface with biomimetic tendon structure is obtained by demolding. (3) Activation treatment of silicone rubber surface: The silicone rubber surface with biomimetic tendril structure obtained in step (2) is subjected to air plasma treatment with a cavity pressure of 400 Pa and an air atmosphere treatment of 300 s to obtain the activated silicone rubber surface with biomimetic tendril structure. (4) Construction of tannic acid-silane pre-coating: 1.0 g of γ-aminopropyltriethoxysilane was pre-dissolved in 20 mL of anhydrous ethanol. 1.0 g of tannic acid was weighed and dissolved in 100 mL of Tris-HCl buffer (10 mM). The pre-dissolved components were then added and magnetically stirred until completely dissolved. The silicone rubber surface with the biomimetic tendril structure activated in step (3) was immersed in the Tris-HCl buffer of tannic acid and γ-aminopropyltriethoxysilane. The pH was adjusted to 8.5 with sodium hydroxide and gently shaken at room temperature for 24 hours. After immersion, the surface was removed, rinsed with deionized water, and dried to construct a tannic acid-silane pre-coating with a biomimetic tendril structure. (5) Construction of copper-tannic acid coordination network: The biomimetic tendril structure with tannic acid-silane pre-coating obtained in step (4) was immersed in copper ions (Cu) 2+ The solution was prepared by gentle shaking at room temperature for 2 hours in a CuSO4·5H2O solution with a concentration of 5 mg / mL. After removal, it was rinsed with deionized water and dried, forming a copper-tannic acid coordination network on the surface of the biomimetic tentacles, which is the biomimetic physical dynamic surface antifouling material.

[0027] Example 4 The preparation method of the biomimetic physical dynamic surface antifouling material described in this embodiment includes the following steps: (1) Preparation of biomimetic tentacle mold: A negative mold of biomimetic tentacle array is processed on a substrate using laser etching technology, i.e., biomimetic tentacle mold; the specific parameters are: laser power 30 W, scanning speed 500 mm / s, repeated scanning 4 times; the structural parameters of the biomimetic tentacle are: diameter 50 μm, length 300 μm, center spacing 200 μm; (2) Preparation of silicone rubber surface by molding: 100 g of hydroxyl-terminated polydimethylsiloxane with a molecular weight of 28000 g / mol, 5 g of polyethyl silicate and 2 g of dibutyltin dilaurate are mixed, stirred thoroughly and degassed under vacuum, and then poured into the biomimetic tendon mold obtained in step (1). The mixture is cured for 24 hours at 25°C and 80% relative humidity. The silicone rubber surface with biomimetic tendon structure is obtained by demolding. (3) Activation treatment of silicone rubber surface: The silicone rubber surface with biomimetic tendril structure obtained in step (2) is subjected to air plasma treatment with a cavity pressure of 400 Pa and an air atmosphere treatment of 300 s to obtain the activated silicone rubber surface with biomimetic tendril structure. (4) Construction of tannic acid-silane pre-coating: 1.0 g of γ-aminopropyltriethoxysilane was pre-dissolved in 20 mL of anhydrous ethanol. 1.0 g of tannic acid was weighed and dissolved in 100 mL of Tris-HCl buffer (10 mM). The pre-dissolved components were then added and magnetically stirred until completely dissolved. The silicone rubber surface with the biomimetic tendril structure activated in step (3) was immersed in the Tris-HCl buffer of tannic acid and γ-aminopropyltriethoxysilane. The pH was adjusted to 8.5 with sodium hydroxide and gently shaken at room temperature for 24 hours. After immersion, the surface was removed, rinsed with deionized water, and dried to construct a tannic acid-silane pre-coating with a biomimetic tendril structure. (5) Construction of copper-tannic acid coordination network: The biomimetic tendril structure with tannic acid-silane pre-coating obtained in step (4) was immersed in copper ions (Cu) 2+ The solution was prepared by gentle shaking at room temperature for 2 hours in a CuCl2·2H2O solution with a concentration of 5 mg / mL. After removal, it was rinsed with deionized water and dried to form a copper-tannic acid coordination network on the surface of the biomimetic tentacles, which is the biomimetic physical dynamic surface antifouling material.

[0028] Example 5 The preparation method of the biomimetic physical dynamic surface antifouling material described in this embodiment includes the following steps: (1) Preparation of biomimetic tentacle mold: A negative mold of biomimetic tentacle array is processed on a substrate using laser etching technology, i.e., biomimetic tentacle mold; the specific parameters are: laser power 30 W, scanning speed 500 mm / s, repeated scanning 4 times; the structural parameters of the biomimetic tentacle are: diameter 50 μm, length 300 μm, center spacing 200 μm; (2) Preparation of silicone rubber surface by molding: 100 g of hydroxyl-terminated polydimethylsiloxane with a molecular weight of 28000 g / mol, 5 g of polyethyl silicate and 2 g of dibutyltin dilaurate are mixed, stirred thoroughly and degassed under vacuum, and then poured into the biomimetic tendon mold obtained in step (1). The mixture is cured for 24 hours at 25°C and 80% relative humidity. The silicone rubber surface with biomimetic tendon structure is obtained by demolding. (3) Activation treatment of silicone rubber surface: The silicone rubber surface with biomimetic tendril structure obtained in step (2) is subjected to air plasma treatment with a cavity pressure of 400 Pa and an air atmosphere treatment of 300 s to obtain the activated silicone rubber surface with biomimetic tendril structure. (4) Construction of tannic acid-silane pre-coating: 1.0 g of γ-aminopropyltriethoxysilane was pre-dissolved in 20 mL of anhydrous ethanol. 1.0 g of tannic acid was weighed and dissolved in 100 mL of Tris-HCl buffer (10 mM). The pre-dissolved components were then added and magnetically stirred until completely dissolved. The silicone rubber surface with the biomimetic tendril structure activated in step (3) was immersed in the Tris-HCl buffer of tannic acid and γ-aminopropyltriethoxysilane. The pH was adjusted to 8.5 with sodium hydroxide and gently shaken at room temperature for 24 hours. After immersion, the surface was removed, rinsed with deionized water, and dried to construct a tannic acid-silane pre-coating with a biomimetic tendril structure. (5) Construction of copper-tannic acid coordination network: The biomimetic tendril structure with tannic acid-silane pre-coating obtained in step (4) was immersed in copper ions (Cu) 2+ The solution was prepared by gentle shaking at room temperature for 2 hours in a Cu(NO3)2·2H2O solution with a concentration of 5 mg / mL. After removal, it was rinsed with deionized water and dried to form a copper-tannic acid coordination network on the surface of the biomimetic tentacles, which is the biomimetic physical dynamic surface antifouling material.

[0029] Example 6 The preparation method of the biomimetic physical dynamic surface antifouling material described in this embodiment includes the following steps: (1) Preparation of biomimetic tentacle mold: A negative mold of biomimetic tentacle array is processed on a substrate using laser etching technology, i.e., biomimetic tentacle mold; the specific parameters are: laser power 30 W, scanning speed 500 mm / s, repeated scanning 4 times; the structural parameters of the biomimetic tentacle are: diameter 50 μm, length 300 μm, center spacing 200 μm; (2) Preparation of silicone rubber surface by molding: 100 g of hydroxyl-terminated polydimethylsiloxane with a molecular weight of 28000 g / mol, 5 g of polyethyl silicate and 2 g of dibutyltin diacetate were mixed, stirred thoroughly and degassed under vacuum, and then poured into the biomimetic tendon mold obtained in step (1). The mixture was cured for 24 hours at 25°C and 80% relative humidity. The silicone rubber surface with biomimetic tendon structure was obtained by demolding. (3) Activation treatment of silicone rubber surface: The silicone rubber surface with biomimetic tendril structure obtained in step (2) is subjected to air plasma treatment with a cavity pressure of 400 Pa and an air atmosphere treatment of 300 s to obtain the activated silicone rubber surface with biomimetic tendril structure. (4) Construction of tannic acid-silane pre-coating: 1.0 g of γ-aminopropyltriethoxysilane was pre-dissolved in 20 mL of anhydrous ethanol. 1.0 g of tannic acid was weighed and dissolved in 100 mL of Tris-HCl buffer (10 mM). The pre-dissolved components were then added and magnetically stirred until completely dissolved. The silicone rubber surface with the biomimetic tendril structure activated in step (3) was immersed in the Tris-HCl buffer of tannic acid and γ-aminopropyltriethoxysilane. The pH was adjusted to 8.5 with sodium hydroxide and gently shaken at room temperature for 24 hours. After immersion, the surface was removed, rinsed with deionized water, and dried to construct a tannic acid-silane pre-coating with a biomimetic tendril structure. (5) Construction of copper-tannic acid coordination network: The biomimetic tendril structure with tannic acid-silane pre-coating obtained in step (4) was immersed in copper ions (Cu) 2+ The solution was prepared by gentle shaking at room temperature for 2 hours in a CuSO4·5H2O solution with a concentration of 5 mg / mL. After removal, it was rinsed with deionized water and dried to form a copper-tannic acid coordination network on the surface of the biomimetic tentacles, which is the biomimetic physical dynamic surface antifouling material.

[0030] Example 7 The preparation method of the biomimetic physical dynamic surface antifouling material described in this embodiment includes the following steps: (1) Preparation of biomimetic tentacle mold: A negative mold of biomimetic tentacle array is processed on a substrate using laser etching technology, i.e., biomimetic tentacle mold; the specific parameters are: laser power 30 W, scanning speed 500 mm / s, repeated scanning 4 times; the structural parameters of the biomimetic tentacle are: diameter 50 μm, length 300 μm, center spacing 200 μm; (2) Preparation of silicone rubber surface by molding: 100 g of hydroxyl-terminated polydimethylsiloxane with a molecular weight of 28000 g / mol, 7 g of polyethyl silicate and 2 g of dibutyltin dilaurate were mixed, stirred thoroughly and degassed under vacuum, and then poured into the biomimetic tendon mold obtained in step (1). The mixture was cured for 24 hours at 25°C and 80% relative humidity. The silicone rubber surface with biomimetic tendon structure was obtained by demolding. (3) Activation treatment of silicone rubber surface: The silicone rubber surface with biomimetic tendril structure obtained in step (2) is subjected to air plasma treatment with a cavity pressure of 400 Pa and an air atmosphere treatment of 300 s to obtain the activated silicone rubber surface with biomimetic tendril structure. (4) Construction of tannic acid-silane pre-coating: 1.0 g of γ-aminopropyltriethoxysilane was pre-dissolved in 20 mL of anhydrous ethanol. 1.0 g of tannic acid was weighed and dissolved in 100 mL of Tris-HCl buffer (10 mM). The pre-dissolved components were then added and magnetically stirred until completely dissolved. The silicone rubber surface with the biomimetic tendril structure activated in step (3) was immersed in the Tris-HCl buffer of tannic acid and γ-aminopropyltriethoxysilane. The pH was adjusted to 8.5 with sodium hydroxide and gently shaken at room temperature for 24 hours. After immersion, the surface was removed, rinsed with deionized water, and dried to construct a tannic acid-silane pre-coating with a biomimetic tendril structure. (5) Construction of copper-tannic acid coordination network: The biomimetic tendril structure with tannic acid-silane pre-coating obtained in step (4) was immersed in copper ions (Cu) 2+ The solution was prepared by gentle shaking at room temperature for 2 hours in a CuSO4·5H2O solution with a concentration of 5 mg / mL. After removal, it was rinsed with deionized water and dried to form a copper-tannic acid coordination network on the surface of the biomimetic tentacles, which is the biomimetic physical dynamic surface antifouling material.

[0031] Example 8 The preparation method of the biomimetic physical dynamic surface antifouling material described in this embodiment includes the following steps: (1) Preparation of biomimetic tentacle mold: A negative mold of biomimetic tentacle array is processed on a substrate using laser etching technology, i.e., biomimetic tentacle mold; the specific parameters are: laser power 30 W, scanning speed 500 mm / s, repeated scanning 4 times; the structural parameters of the biomimetic tentacle are: diameter 50 μm, length 300 μm, center spacing 200 μm; (2) Preparation of silicone rubber surface by molding: 100 g of hydroxyl-terminated polydimethylsiloxane with a molecular weight of 28000 g / mol, 3 g of polyethyl silicate and 2 g of dibutyltin dilaurate are mixed, stirred thoroughly and degassed under vacuum, and then poured into the biomimetic tendon mold obtained in step (1). The mixture is cured for 24 hours at 25°C and 80% relative humidity. The silicone rubber surface with biomimetic tendon structure is obtained by demolding. (3) Activation treatment of silicone rubber surface: The silicone rubber surface with biomimetic tendril structure obtained in step (2) is subjected to air plasma treatment with a cavity pressure of 400 Pa and an air atmosphere treatment of 300 s to obtain the activated silicone rubber surface with biomimetic tendril structure. (4) Construction of tannic acid-silane pre-coating: 1.0 g of γ-aminopropyltriethoxysilane was pre-dissolved in 20 mL of anhydrous ethanol. 1.0 g of tannic acid was weighed and dissolved in 100 mL of Tris-HCl buffer (10 mM). The pre-dissolved components were then added and magnetically stirred until completely dissolved. The silicone rubber surface with the biomimetic tendril structure activated in step (3) was immersed in the Tris-HCl buffer of tannic acid and γ-aminopropyltriethoxysilane. The pH was adjusted to 8.5 with sodium hydroxide and gently shaken at room temperature for 24 hours. After immersion, the surface was removed, rinsed with deionized water, and dried to construct a tannic acid-silane pre-coating with a biomimetic tendril structure. (5) Construction of copper-tannic acid coordination network: The biomimetic tendril structure with tannic acid-silane pre-coating obtained in step (4) was immersed in copper ions (Cu) 2+ The solution was prepared by gentle shaking at room temperature for 2 hours in a CuSO4·5H2O solution with a concentration of 5 mg / mL. After removal, it was rinsed with deionized water and dried to form a copper-tannic acid coordination network on the surface of the biomimetic tentacles, which is the biomimetic physical dynamic surface antifouling material.

[0032] Comparative Example 1 (1) Preparation of biomimetic tentacle mold: A negative mold of biomimetic tentacle array is processed on a substrate using laser etching technology, i.e., biomimetic tentacle mold; the specific parameters are: laser power 30 W, scanning speed 500 mm / s, repeated scanning 4 times; the structural parameters of the biomimetic tentacle are: diameter 50 μm, length 300 μm, center spacing 200 μm; (2) Preparation of silicone rubber surface by molding: 100 g of hydroxyl-terminated polydimethylsiloxane with a molecular weight of 28000 g / mol, 5 g of polyethyl silicate and 2 g of dibutyltin dilaurate are mixed, stirred thoroughly and degassed under vacuum, and then poured into the biomimetic tentacle mold obtained in step (1). The mixture is cured for 24 hours at 25°C and 80% relative humidity. The silicone rubber surface with biomimetic tentacle structure is obtained by demolding.

[0033] Because the surface only possesses a biomimetic tentacle-like physical structure and lacks a copper-tannic acid chemical bactericidal network, it cannot effectively inhibit the initial attachment and growth of microorganisms under static or low-flow conditions. Experimental tests showed that the sample's 24-hour antibacterial rate against marine bacteria (such as Pseudomonas aeruginosa) was less than 10%, and after 7 days of static incubation, a large-area biofilm formed on the surface, completely losing its antifouling ability, proving that a purely physical structure cannot cope with low-flow conditions.

[0034] In this embodiment, the contact angle results of the biomimetic dynamic surface antifouling material based on laser etching physical structure are as follows: Figure 3 As shown in (b). The sterilization (Pseudomonas aeruginosa) effect of the biomimetic physical dynamic surface antifouling material based on laser etching physical structure described in this embodiment is illustrated in the photograph. Figure 4 As shown in (b).

[0035] Comparative Example 2 (1) Preparation of silicone rubber surface: 100 g of hydroxyl-terminated polydimethylsiloxane with a molecular weight of 28000 g / mol, 5 g of polyethyl silicate and 2 g of dibutyltin dilaurate were mixed, stirred thoroughly and degassed under vacuum, and then poured into a flat-bottomed smooth mold. The mixture was cured for 24 hours at 25°C and 80% relative humidity. The silicone rubber surface with a planar structure was obtained by demolding.

[0036] (2) Silicone rubber surface activation treatment: The silicone rubber bionic tentacles obtained in step (2) are placed in a plasma cleaner and treated with air atmosphere for 300 s with a chamber pressure of 400 Pa.

[0037] (3) Activation treatment of silicone rubber surface: The silicone rubber surface with planar structure obtained in step (2) is subjected to air plasma treatment with a chamber pressure of 400 Pa and an air atmosphere treatment of 300 s to obtain an activated silicone rubber surface with planar structure. (4) Construction of tannic acid-silane pre-coating: 1.0 g of γ-aminopropyltriethoxysilane was pre-dissolved in 20 mL of anhydrous ethanol. 1.0 g of tannic acid was weighed and dissolved in 100 mL of Tris-HCl buffer (10 mM). The pre-dissolved components were then added and magnetically stirred until completely dissolved. The planar silicone rubber surface activated in step (3) was immersed in the Tris-HCl buffer of tannic acid and γ-aminopropyltriethoxysilane. The pH was adjusted to 8.5 with sodium hydroxide. The mixture was gently shaken at room temperature for 24 hours. After immersion, the surface was removed, rinsed with deionized water, and dried to construct a tannic acid-silane pre-coating with a biomimetic tendril structure. (5) Construction of copper-tannic acid coordination network: The planar structure with tannic acid-silane pre-coating obtained in step (4) is immersed in copper ions (Cu) 2+The solution was prepared by gentle shaking at room temperature for 2 hours in a CuSO4·5H2O solution with a concentration of 5 mg / mL. After removal, it was rinsed with deionized water and dried to form a copper-tannic acid coordination network on the surface of the planar silicone rubber, thus obtaining an antifouling material with only a copper-tannic acid coordination network.

[0038] Because the surface is planar and lacks the large-scale collaborative cleaning characteristics of biomimetic tentacles, it cannot produce effective physical cleaning at high flow rates. Tests showed that the sample, at a flow rate of 1 m / s, was ineffective against attached *Navicula* (a type of algae). N.incerta The desorption efficiency of macrofouling is less than 30%, and the biofouling organisms are firmly attached to the surface, proving that chemical sterilization alone cannot effectively remove the formed macrofouling. The antifouling method is singular and the overall performance is limited.

[0039] Performance testing The performance of the biomimetic physical dynamic surface antifouling materials prepared in Examples 1 to 8 and Comparative Examples 1 to 2 was tested under the following conditions: (1) At 25°C, tensile tests were performed using an Instron 5966 general mechanical testing machine with a 10 kN load sensor to evaluate mechanical properties.

[0040] (2) At 25°C, use the Theta Auto 113 contact angle tester to drop 4 μL of deionized water onto the material surface, observe and record the contact angle size.

[0041] (3) Under static conditions at 25℃, the prepared material (cut into 1x1 cm pieces) 2 Immerse 1 mL of a 10% concentration 7 CFU / mL of marine Pseudomonas aeruginosa ( Pseudomonas In a suspension containing (sp.), the bacteria were co-incubated with the material at room temperature for 4 h, followed by gentle rinsing with artificial seawater to remove unadhered bacteria. The suspension was sonicated for 1 min, and strongly adherent bacteria were collected. 100 μL of the collected suspension was spread onto an agar plate and incubated at 30°C for 24 h. Colony counts were performed using Image-J software, and analysis was conducted using Origin.

[0042] (4) Diatoms produced by Xiamen University were selected. Navicula incerta ( N.incerta The samples were cultured in F / 2 medium at 23°C under a 12:12 light / dark cycle. The samples were placed in clean, sterile beakers and immersed in a diatom suspension with a chlorophyll concentration of 0.25 μg / L. Co-culture was performed for 2 weeks to allow a visible algal film to deposit on the sample surface. The samples were then placed in a pre-built vortex flushing device and flushed at a flow rate of 1 m / s for 10 minutes. The area of ​​remaining algae was counted using Image-J and analyzed using Origin.

[0043] Table 1 below shows the performance test data of the biomimetic physical dynamic surface antifouling materials prepared in Examples 1 to 8 and Comparative Examples 1 to 2.

[0044] Table 1 shows the performance indicators of the materials prepared in Examples 1 to 8 and Comparative Examples 1 to 2.

[0045] As can be seen from Examples 1 to 8 and Comparative Examples 1 to 2, Examples 1 to 8 of this invention, while maintaining a low elastic modulus (all <1 MPa) to ensure that the biomimetic tentacles can undergo significant and effective deformation under water flow, reduce the water contact angle from 114.5° before modification to below 70° through surface tannic acid-copper coordination network modification, and achieve a bactericidal rate of over 98% against Pseudomonas aeruginosa. The algae removal rate is closely related to the elastic modulus of the tentacles. By changing the proportion of the curing agent between 0 and 10 parts, the algae removal rate in Examples 1 to 8 can all be greater than 75%. Comparative Example 1 (only having a physical structure) has excellent dynamic anti-algae performance, but due to the lack of a chemical bactericidal network, the static bactericidal rate is less than 10%; Comparative Example 2 (only having a chemical bactericidal network) has excellent static bactericidal performance, but lacks a physical dynamic structure, and its anti-algae rate is less than 30%, and it cannot effectively remove attached macrofouling. The overall antifouling effect of Examples 1 to 8 is better than that of Comparative Examples 1 and 2.

[0046] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A method for preparing a biomimetic physical dynamic surface antifouling material, characterized in that, Includes the following steps: (1) Preparation of biomimetic tentacle mold: Using laser etching technology, a negative mold of biomimetic tentacle array is processed on a substrate, namely biomimetic tentacle mold; the structural parameters of the biomimetic tentacle are: diameter 50~200 μm, length 100~300 μm, and center spacing is 2~10 times the diameter. (2) Preparation of silicone rubber surface by molding: The double-hydroxyl-terminated polydimethylsiloxane, crosslinking agent and catalyst are mixed in a mass ratio of 100: 1~10: 0.5~2. After thorough stirring and vacuum degassing, the mixture is poured into the biomimetic tendril mold obtained in step (1), cured at room temperature and demolded to obtain a silicone rubber surface with a biomimetic tendril structure. (3) Activation treatment of silicone rubber surface: The silicone rubber surface with biomimetic tendril structure obtained in step (2) is subjected to air plasma treatment to obtain activated silicone rubber surface with biomimetic tendril structure. (4) Construction of tannic acid-silane pre-coating: The silicone rubber surface of the biomimetic tendril structure activated in step (3) was immersed in a Tris-HCl buffer solution of tannic acid and γ-aminopropyltriethoxysilane, gently shaken at room temperature, removed after immersion, rinsed with deionized water and dried to construct a tannic acid-silane pre-coating with biomimetic tendril structure. (5) Construction of copper-tannic acid coordination network: The biomimetic tendril structure with tannic acid-silane pre-coating obtained in step (4) is immersed in copper salt solution, taken out, rinsed with deionized water and dried, and a copper-tannic acid coordination network is formed on the surface of the biomimetic tendril to prepare a biomimetic physical dynamic surface antifouling material.

2. The method for preparing the biomimetic physical dynamic surface antifouling material according to claim 1, characterized in that, The substrate mentioned in step (1) is one of stainless steel plate, aluminum plate or silicon wafer.

3. The method for preparing the biomimetic physical dynamic surface antifouling material according to claim 1, characterized in that, The laser etching power in step (1) is 20~200 W, the scanning speed is 200~500 mm / s, and the number of repeated scans is 1~6.

4. The method for preparing the biomimetic physical dynamic surface antifouling material according to claim 1, characterized in that, The molecular weight of the hydroxyl-terminated polydimethylsiloxane in step (2) is 26,000 to 30,000 g / mol; the crosslinking agent is polyethyl silicate; and the catalyst is one of dibutyltin dilaurate, stannous octoate, dibutyltin diacetate, tetraisopropyl titanate, or tetrabutyl titanate.

5. The method for preparing the biomimetic physical dynamic surface antifouling material according to claim 1, characterized in that, In step (3), the cavity pressure of the air plasma treatment is 300-500 Pa, the power of the air plasma treatment is 100-400 W, and the time of the air plasma treatment is 300-600 seconds.

6. The method for preparing the biomimetic physical dynamic surface antifouling material according to claim 1, characterized in that, The Tris-HCl buffer solution of tannic acid and γ-aminopropyltriethoxysilane mentioned in step (4) is prepared by first dissolving γ-aminopropyltriethoxysilane in anhydrous ethanol, and then dissolving tannic acid in Tris-HCl buffer solution to adjust the pH to 7-10; the concentration of the Tris-HCl buffer solution is 10~50 mM; the mass concentration of tannic acid is 0.5~20 mg / mL; and the mass ratio of γ-aminopropyltriethoxysilane to tannic acid is 0.2~5:

1.

7. The method for preparing the biomimetic physical dynamic surface antifouling material according to claim 1, characterized in that, The copper salt solution mentioned in step (5) is any one of copper sulfate, copper chloride, and copper nitrate solutions; the concentration of copper ions in the copper salt solution is 1~20 mg / mL.

8. A biomimetic physical dynamic surface antifouling material, characterized in that, It is prepared according to any one of the preparation methods in claims 1 to 7.

9. The biomimetic physical dynamic surface antifouling material according to claim 8, characterized in that, The biomimetic physical dynamic surface antifouling material has an elastic modulus of 0.3~1.5 MPa, a water contact angle of 55~75°, and a 24-hour antibacterial rate of not less than 90% against Pseudomonas aeruginosa.

10. The application of a biomimetic physical dynamic surface antifouling material according to claim 8 or 9 in the field of marine antifouling, characterized in that, Specifically, the application involves using biomimetic physical dynamic surface antifouling materials on ship hulls, offshore platform structures, underwater sensors, aquaculture cages, or seawater pipeline systems.

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