Super-smooth antifouling surface with photo-thermal self-repairing performance as well as preparation method and application of super-smooth antifouling surface

Abstract

The invention provides a super-smooth antifouling surface with photo-thermal self-repairing performance as well as a preparation method and application of the super-smooth antifouling surface. The super-lubricity antifouling surface comprises a light response substrate and a lubricating layer formed on the light response substrate. Wherein the photoresponse substrate can trigger the photothermal conversion performance under the irradiation of near-infrared light, so that the temperature of the super-lubricity antifouling surface is rapidly increased, polyethylene wax and C12-C16 long-chain alkane in the lubricating layer can be in a molten state, the position, with defects, of the surface of coastal or marine common mechanical equipment is filled up, and after cooling, the surface of the mechanical equipment is not damaged. And a self-repairing function is realized. Compared with the prior art, by compounding the polyethylene wax and the C12-C16 long-chain alkane, a novel solid-state phase-change super-smooth surface can be provided, the stability and the antifouling property of the super-smooth antifouling surface are remarkably improved, and the problem that the antifouling property fails due to the fact that a traditional liquid-state super-smooth surface lubricating layer is poor in shear resistance is remarkably solved.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of marine antifouling, and particularly relates to a super-slippery antifouling surface with photothermal self-repairing performance and a preparation method and application thereof. BACKGROUND

[0002] Marine biofouling refers to the phenomenon that harmful molecules, microorganisms, plants and animals adhere to the surface of a ship body and seabed equipment. Studies have shown that the fouling organisms growing on the ship body can accelerate surface corrosion, damage the propeller and increase the resistance, thereby causing high fuel consumption and high maintenance costs, and the fouling organisms adhering to the seawater cage infrastructure damage the seawater aquaculture, shorten the service life of the equipment and reduce the yield. Therefore, marine biofouling has caused considerable economic losses to the related industries and is a major obstacle to the efficient and sustainable production development. In addition, the operation of underwater coastal marine structures, including cross-sea bridge supports and wharfs, as well as offshore facilities such as oil fields, can be affected; the mechanical equipment can be structurally damaged or destroyed, and offshore oil production can be limited and can be endangered due to biofouling.

[0003] To solve the above problems, the traditional method generally coats the surface of a ship body with antifouling paint, which is composed of chemically active compounds such as silver, copper and tributyltin (TBT). However, the paint lacks specificity and has high toxicity to fouling organisms and non-target marine organisms, thereby causing seawater pollution. Therefore, the development of new environmentally friendly antifouling paint has attracted widespread attention from many scholars.

[0004] Bionic super-slippery surface (SLIPS) includes a substrate and a lubricating layer, which can "fix" a dynamic liquid surface on a structured rough substrate by simulating the principle that a pitcher plant captures prey with a smooth liquid film on the surface. Studies have shown that SLIPS can effectively repel various liquids, quickly restore liquid repellency after physical damage, resist ice and pollutant adhesion, and can withstand high pressure, and has great application potential in the field of marine antifouling. However, the service life of the traditional SLIPS is short, the shear resistance is weak, it is difficult to cope with the complex marine environment in the actual sea, and the lubricating layer is easy to flow out, thereby causing the antifouling performance to fail. SUMMARY

[0005] Therefore, the purpose of the present application is to provide a super-slippery antifouling surface with photothermal self-repairing performance and a preparation method and application thereof.

[0006] To achieve this purpose, the present application adopts the following technical solutions:

[0007] In a first aspect, the present invention provides an ultra-slip anti-fouling surface with photothermal self-repairing properties, comprising a photoresponsive substrate and a lubricating layer formed on the photoresponsive substrate;

[0008] The raw materials for preparing the lubricating layer include polyethylene wax and C12-C16 alkanes.

[0009] Preferably, the mass ratio of the polyethylene wax to the C12-C16 alkane is (1-3):9.

[0010] Preferably, the C12-C16 alkane includes any one of dodecane, tetradecane or hexadecane.

[0011] Preferably, the photoresponsive substrate comprises a substrate body and a functional auxiliary agent layer formed on the substrate body.

[0012] Preferably, the raw materials for preparing the functional auxiliary agent layer include an antibacterial agent coated with a light-responsive substance and a mesoporous material loaded with an antifouling agent.

[0013] Preferably, the antibacterial agent coated with the photoresponsive substance is hydrophobically modified.

[0014] Preferably, the hydrophobic agent used for the hydrophobic modification is selected from any one or more of stearic acid, perfluorodecyltrimethoxysilane or γ-aminopropyltriethoxysilane.

[0015] Preferably, the substrate body comprises any one or more of polyurethane, epoxy resin or polyurea.

[0016] Preferably, the light-responsive substance is formed by polymerization of dopamine hydrochloride and tris(hydroxymethyl)aminomethane on the surface of the antibacterial agent.

[0017] Preferably, the antibacterial agent includes any one or more of zinc oxide, flower-shaped zinc oxide or spherical zinc oxide.

[0018] Preferably, the antifouling agent includes any one or more of bromopyrrolecarbonitrile, chitosan quaternary ammonium salt or benzisothiazolinone.

[0019] Preferably, the mesoporous material includes any one or more of mesoporous silica, hollow mesoporous silica or mesoporous silica.

[0020] In a second aspect, the present invention provides a method for preparing the above-mentioned ultra-slip and anti-fouling surface, comprising the following steps:

[0021] S1: Provide photoresponsive substrate;

[0022] S2: heating and melting polyethylene wax and C12-C16 alkanes and mixing them, contacting the mixture with the surface of the photoresponsive substrate in step S1, and cooling the mixture to obtain an ultra-slip and anti-fouling surface.

[0023] Preferably, the light-responsive substrate is prepared by the following method:

[0024] (1) coating the substrate bulk solution on the surface of the preheated carrier and heating to a semi-cured state;

[0025] (2) mixing the light-responsive substance coated antibacterial agent and the mesoporous material loaded antifouling agent with the solvent to obtain a mixed solution, introducing it into the semi-cured product obtained in step (1), and solidifying to obtain the light-responsive substrate;

[0026] The light-responsive substance is formed by polymerization of dopamine hydrochloride and tris(hydroxymethyl) aminomethane on the surface of the antibacterial agent.

[0027] Preferably, the mass ratio of dopamine hydrochloride, tris(hydroxymethyl) aminomethane and antibacterial agent is (2-3):(1-1.5):(1-1.5).

[0028] Preferably, the mass ratio of the antifouling agent and the mesoporous material is (2-4):(1-1.5).

[0029] Preferably, the light-responsive substance coated antibacterial agent is a light-responsive substance coated antibacterial agent modified by a hydrophobic agent; the mass ratio of the hydrophobic agent, dopamine hydrochloride, tris(hydroxymethyl) aminomethane and antibacterial agent is (0.5-1):(2-3):(1-1.5):(1-1.5).

[0030] In a third aspect, the application provides a use of the above-mentioned super-smooth antifouling surface in the field of anti-marine biofouling.

[0031] Compared with the prior art, the application has the following beneficial effects:

[0032] The application provides a super-smooth antifouling surface with photothermal self-repairing performance, which comprises a light-responsive substrate and a lubricating layer formed on the light-responsive substrate. The light-responsive substrate can trigger photothermal conversion performance under near-infrared light irradiation, so that the temperature of the super-smooth antifouling surface rises rapidly, thereby making the polyethylene wax and C12-C16 long-chain alkanes in the lubricating layer present a molten state, and then filling the positions where defects occur on the surface of mechanical equipment commonly used along the coast or in the sea, and realizing the self-repairing function after cooling. Compared with the prior art, the application can provide a new solid phase change super-smooth surface by compounding polyethylene wax and C12-C16 long-chain alkanes, significantly improve the stability and antifouling performance of the super-smooth antifouling surface, and significantly improve the problems such as failure of antifouling performance caused by weak shear resistance of the lubricating layer of the traditional liquid super-smooth surface. BRIEF DESCRIPTION OF DRAWINGS

[0033] Figure 1This is the FTIR spectrum of the polyurethane base material prepared in Example 1;

[0034] Figure 2 These are SEM images of the flower-shaped nano-zinc oxide, the polydopamine-coated flower-shaped nano-zinc oxide, and the hydrophobic polydopamine-coated flower-shaped nano-zinc oxide obtained in Example 2;

[0035] Among them, (a1) and (a2) correspond to flower-like nano-zinc oxide; (b1) and (b2) correspond to polydopamine-coated flower-like nano-zinc oxide; (c1) and (c2) correspond to hydrophobic polydopamine-coated flower-like nano-zinc oxide;

[0036] Figure 3 The XRD spectra of the flower-shaped nano zinc oxide, the polydopamine-coated flower-shaped nano zinc oxide, and the hydrophobic polydopamine-coated flower-shaped nano zinc oxide obtained in Example 2 are shown;

[0037] Figure 4 FTIR spectra of ZnO, SA, ZnO@PDA, and ZnO@PDA@SA;

[0038] Figure 5 XPS spectra of ZnO@PDA and ZnO@PDA@SA;

[0039] Figure 6 TG graph and FTIR curve of mesoporous silica and mesoporous silica loaded with antifouling agent Tra;

[0040] Among them, (a) corresponds to the TG graph, (b) corresponds to the FTIR curve graph;

[0041] Figure 7 TEM images and EDS images of mesoporous silica and mesoporous silica loaded with antifouling agent Tra;

[0042] Among them, a1, a2 are TEM low-magnification and high-magnification images of original mesoporous silica, a3, a4 are TEM low-magnification and high-magnification images of mesoporous silica loaded with antifouling agent Tra, a5, a6 are EDS images (F and N elements) of the surface of mesoporous silica loaded with antifouling agent Tra;

[0043] Figure 8 Curves of water contact angle and sliding angle on the surface of lubricating layer constructed with different ratios of polyethylene wax and tetradecane;

[0044] Among them, (a) corresponds to the water contact angle, and (b) corresponds to the sliding angle;

[0045] Figure 9 Macroscopic images of the state stability of solid phase change lubricating layers at different ratios after heating, melting, mixing, cooling, inversion, and shaking;

[0046] Figure 10 The photothermal heating curve and optical image of the photothermal repair of the supersmooth surface obtained in Example 4;

[0047] Among them, (a) corresponds to the photothermal heating curve; (b) corresponds to the optical image of the scratched surface of the sample after artificial damage; (c) corresponds to the optical image of the damaged area heating up and melting under near-infrared light irradiation; (d) corresponds to the optical image of the damaged area after the light source is removed and cooled, and the damaged area is repaired;

[0048] Figure 11 These are the antifouling test results of the blank glass sample and the ultra-slip antifouling surface sample obtained in Example 4;

[0049] Among them, (a) corresponds to the anti-adhesion test result of bovine serum albumin, (b) corresponds to the anti-fouling test result of Escherichia coli, (c) corresponds to the anti-fouling test result of Staphylococcus aureus, (d) corresponds to the anti-fouling test result of Chlorella vulgaris, and (e) corresponds to the anti-fouling test result of Pseudoalteromonas.

[0050] BS corresponds to the blank glass sample without coating; PCS corresponds to the ultra-slip antifouling surface obtained in Example 4. DETAILED DESCRIPTION

[0051] The following will clearly and completely describe the technical solutions of the present invention in conjunction with the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0052] The present invention provides an ultra-slip antifouling surface with photothermal self-healing properties, comprising a photoresponsive substrate and a lubricating layer formed on the substrate. The photoresponsive substrate comprises a substrate body and a roughened functional additive layer formed on the substrate body; the functional additive layer is prepared from raw materials including an antibacterial agent coated with a photoresponsive substance and a mesoporous material loaded with an antifouling agent.

[0053] In the present invention, the antibacterial agent coated with the photoresponsive substance is preferably hydrophobically modified; the hydrophobic agent used for the hydrophobic modification is selected from any one or more of stearic acid, perfluorodecyltrimethoxysilane or γ-aminopropyltriethoxysilane.

[0054] In the present invention, the photoresponsive substrate can promote the rapid heating of the lubricating layer under the irradiation of near-infrared light, so that the raw materials for preparing the lubricating layer (polyethylene wax and C12-C16 alkanes) are in a melted state, and can then flow and fill the defects on the surface of mechanical equipment commonly used in coastal or marine areas. After cooling, the self-repair function can be realized.

[0055] It should be noted that the present invention conducted experiments on compounding multiple components for the setting of the lubricating layer and found that:

[0056] Polyethylene wax + C12-C16 alkane (preferably tetradecane): The system has good compatibility and excellent surface droplet sliding performance after compounding.

[0057] Polyethylene wax + dimethyl silicone oil: The system has poor compatibility, is immiscible, and the system separates into layers in the molten state.

[0058] Paraffin + tetradecane: poor compatibility, the system separates into layers in the molten state.

[0059] Beeswax + tetradecane: good compatibility in the molten state, but poor surface droplet sliding performance.

[0060] Therefore, after screening and optimization, the present invention uses polyethylene wax + C12-C16 alkanes as the raw materials of the lubricating layer.

[0061] The present invention also provides a method for preparing the above-mentioned super-slip and anti-fouling surface, comprising the following steps:

[0062] S1: Provide photoresponsive substrate;

[0063] S2: Polyethylene wax and C12-C16 alkanes are heated, melted, and mixed, and then added dropwise to the surface of the photoresponsive substrate in step S1. After cooling, an ultra-slip and anti-fouling surface is obtained.

[0064] According to the present invention, a photoresponsive substrate is first provided.

[0065] In the present invention, the photoresponsive substrate can be prepared according to the following method:

[0066] (1) coating the substrate bulk solution on the preheated carrier surface and heating it to a semi-cured state;

[0067] (2) The antibacterial agent coated with the photoresponsive substance and the mesoporous material loaded with the antifouling agent are mixed with a solvent to obtain a mixed solution, which is introduced into the semi-cured product obtained in step (1) and cured to obtain a photoresponsive substrate.

[0068] In the present invention, the substrate body comprises any one or more of polyurethane, polyurea or epoxy resin, preferably polyurethane. The present invention has no particular limitation on the preparation method of the polyurethane substrate, and the method can be carried out according to methods well known to those skilled in the art.

[0069] In some embodiments of the present invention, the substrate is preferably dissolved in a solvent, such as anhydrous ethanol, and coated on a preheated carrier (e.g., Q235 carbon steel) at 50-60°C for 20-30 minutes until it is semi-cured. The coating is preferably sprayed using a spray gun.

[0070] Then, according to the present invention, the antibacterial agent coated with the photoresponsive substance and the mesoporous material loaded with the antifouling agent are mixed with a solvent to obtain a mixed solution, which is introduced into the semi-cured product obtained in step (1) and cured to obtain a photoresponsive substrate.

[0071] Among them, the antibacterial agent coated with the photoresponsive substance and the mesoporous material loaded with the antifouling agent need to be prepared separately.

[0072] In the present invention, the photoresponsive substance is formed by directly polymerizing dopamine hydrochloride and tris(hydroxymethyl)aminomethane on the surface of the antibacterial agent; the antibacterial agent includes any one or more of zinc oxide, flower-shaped zinc oxide or spherical zinc oxide, preferably flower-shaped zinc oxide with a larger specific surface area, and more preferably flower-shaped nano zinc oxide.

[0073] In some embodiments of the present invention, taking polydopamine-coated flower-shaped nano zinc oxide as an example, the preparation method includes the following steps:

[0074] 1) Dissolve 6 g of zinc nitrate hexahydrate and 15 g of sodium citrate dihydrate in 400 mL of deionized water, slowly add 80 mL of 1.5 M sodium hydroxide at a constant rate, and continue stirring for 30 minutes. After the reaction is completed, wash with deionized water and filter three times, and finally dry at 60°C to constant weight to obtain flower-shaped nano zinc oxide.

[0075] 2) 1 g of the above-mentioned flower-shaped nano-zinc oxide product was ultrasonically dispersed in 400 mL of deionized water, and then 0.4 g of dopamine hydrochloride and 0.4 g of tris(hydroxymethyl)aminomethane were added and stirred at room temperature for 2 h. After the reaction was completed, it was washed with deionized water and filtered three times, and finally dried at 60°C to constant weight to obtain polydopamine-coated flower-shaped nano-zinc oxide.

[0076] The parameters involved in the above preparation method can be adjusted accordingly within a reasonable range of variation.

[0077] In some preferred embodiments of the present invention, the antibacterial agent coated with the photoresponsive substance can be hydrophobically modified, and the hydrophobic agent used can be any one or more of stearic acid, perfluorodecyltrimethoxysilane or γ-aminopropyltriethoxysilane.

[0078] Taking polydopamine-coated flower-shaped nano zinc oxide as an example, hydrophobic modification thereof includes the following steps:

[0079] 1 g of polydopamine-coated flower-shaped nano-zinc oxide was ultrasonically dispersed in 20 mL of anhydrous ethanol, and then 0.25 g of stearic acid was added and stirred at room temperature for 2 h. After the reaction was completed, it was washed with anhydrous ethanol and filtered three times, and finally dried at 60°C to constant weight.

[0080] The parameters involved in the above method can be adjusted within a reasonable range.

[0081] In the present application, the antifouling agent comprises any one or more of bromopyrollite, chitosan quaternary ammonium salt or benzisothiazolinone; and the mesoporous material comprises any one or more of mesoporous silica, hollow mesoporous silica or mesoporous silica.

[0082] In some embodiments of the present application, taking the mesoporous silica loaded with bromopyrollite as an example, the mesoporous silica loaded with bromopyrollite can be prepared according to the following method:

[0083] 1) 0.3 g of mesoporous silica is ultrasonically dispersed in 30 mL of anhydrous methanol, and the air in the pores is removed by vacuum;

[0084] 2) Then 0.9 g of bromopyrollite is added to the above solution, and after ultrasonic dissolution, it is sealed and continuously stirred for 24 h;

[0085] 3) After the stirring is completed, it is washed with anhydrous ethanol and suction filtered three times, and the product is dried at room temperature to a constant weight.

[0086] The parameters involved in the above method can be adjusted within a reasonable range.

[0087] In the present application, after obtaining the light-responsive substance-coated antibacterial agent and the mesoporous material loaded with the antifouling agent, the light-responsive substance-coated antibacterial agent and the mesoporous material loaded with the antifouling agent are ultrasonically dispersed in 5 mL of an ethanol solution, and are sprayed onto the surface of the above-mentioned substrate body in a semi-cured state using an airbrush, and are cured at room temperature for 24 h to obtain a light-responsive substrate.

[0088] After obtaining the light-responsive substrate, according to the present application, the polyethylene wax and the C12-C16 alkane are heated and melted to mix, and then are contacted with the surface of the light-responsive substrate in step S1, preferably are added dropwise on the surface of the light-responsive substrate in step S1, and after cooling, a super-smooth antifouling surface is obtained.

[0089] In the present application, the C12-C16 alkane comprises any one of dodecane, tetradecane or hexadecane, and preferably is tetradecane. The mass ratio of the polyethylene wax and the C12-C16 alkane is (1-3):9, and specifically, the C12-C16 alkane can account for 75%, 80%, 85% or 90% or the like of the total mass of the polyethylene wax and the C12-C16 alkane.

[0090] In some embodiments of the present application, the polyethylene wax and the C12-C16 alkane are preferably heated and melted to mix according to the mass ratio; then the obtained mixed solution is added dropwise to the surface of a preheated rough substrate, and after soaking and cooling, a self-repairing solid phase change super-smooth surface with light-heat performance is obtained.

[0091] In summary, the present invention preferably uses a polyurethane material with self-repairing properties by introducing dynamic disulfide bonds and strong hydrogen bonds as a substrate, and imparts light-responsiveness and bactericidal properties to the substrate by introducing a bactericide coated with a light-responsive substance on the surface of the substrate. At the same time, the light-responsive substance-coated bactericide can improve the rough structure of the substrate and improve its bonding properties. Furthermore, by introducing a mesoporous material loaded with an antifouling agent and inserting it into the rough structure, its antifouling and bactericidal properties are further improved, and chemical sterilization and physical antifouling are organically combined. Among them, the presence of the mesoporous material can efficiently load the antifouling agent and at the same time construct a complex multi-layer rough structure with the flower-shaped zinc oxide. Finally, the present invention provides a lubricating layer obtained by compounding polyethylene wax and C12 to C16 alkanes on the substrate, which can construct a stable solid phase change lubricating layer and impart super-slip antifouling and phase change properties to the surface.

[0092] Based on the above, the present invention also provides an application of the ultra-slip antifouling surface described in the aforementioned technical solution for use in the field of marine biofouling prevention. The results showed that the prepared ultra-slip antifouling surface exhibited excellent self-healing properties under near-infrared light irradiation and exhibited excellent anti-adhesion effects against Pseudomonas aeruginosa and Chlorella vulgaris.

[0093] In order to further illustrate the present invention, the following examples are provided for detailed description. The experimental raw materials used in the following examples of the present invention are all commonly available commercial products.

[0094] Example 1 - Synthesis of self-repairing polyurethane substrate material

[0095] The reactants include: polytetrahydrofuran (Mn-1000), 1,4-butanediol, 4,4'-diaminodiphenyl disulfide, isophorone diisocyanate, and dibutyltin dilaurate, wherein the molar ratio of polytetrahydrofuran: 4,4'-diaminodiphenyl disulfide: 1,4-butanediol: isophorone diisocyanate is 4:1.5:1.5:1.

[0096] The synthetic preparation process is as follows:

[0097] Under nitrogen atmosphere, 0.1 mol of polytetrahydrofuran and 0.4 mol of isophorone diisocyanate were dissolved in an appropriate amount of anhydrous tetrahydrofuran solvent, 0.05 g of dibutyltin dilaurate was added, and the mixture was reacted at 70° C. for 2 h.

[0098] Subsequently, 0.15 mol of diaminodiphenyl disulfide and 0.15 mol of butanediol were dissolved in an appropriate amount of anhydrous tetrahydrofuran, added to the reaction system under a nitrogen atmosphere, and the reaction was continued for 4 hours.

[0099] After the reaction is completed, the product is poured into a polytetrafluoroethylene mold and dried at 6°C for 24 hours to obtain a polyurethane base material with better self-healing properties.

[0100] The FTIR spectrum of the polyurethane base material prepared in this embodiment is as follows: Figure 1 As shown in the figure, 2-DTDA is 4,4'-diaminodiphenyl disulfide, IPDI is isophorone diisocyanate, BDO is 1,4-butanediol, PTMEG is polytetrahydrofuran, and PU is a synthetic polyurethane. By comparing the FTIR spectra of PU and IPDI, it is found that the corresponding chromophore of IPDI is located at about 2262cm -1 The characteristic absorption peak of the NCO group at 3353 cm-1 completely disappears in the spectrum of PU. -1 and 1712cm -1 The characteristic peaks of -NH and -C=O groups appeared at 518 cm, indicating that the -NCO group had reacted completely and formed a carbamate group. -1 The characteristic peak of the SS bond at still exists in the PU spectrum, which indicates the successful synthesis of the designed polyurethane product.

[0101] Example 2 - Construction of a hydrophobized rough substrate with self-healing properties

[0102] 1. Preparation of hydrophobic polydopamine-coated flower-shaped nano-zinc oxide:

[0103] 1) Dissolve 6 g of zinc nitrate hexahydrate and 15 g of sodium citrate dihydrate in 400 mL of deionized water, slowly add 80 mL of 1.5 M sodium hydroxide at a constant rate, and continue stirring for 30 minutes. After the reaction is completed, wash with deionized water and filter three times, and finally dry at 60 ° C to constant weight to obtain flower-shaped nano zinc oxide, the SEM image of which is shown as follows: Figure 2 As shown in (a1) and (a2).

[0104] 2) 1 g of the above flower-like zinc oxide product was ultrasonically dispersed in 400 mL of deionized water, and then 0.4 g of dopamine hydrochloride and 0.4 g of tris(hydroxymethyl)aminomethane were added and stirred at room temperature for 2 h. After the reaction was completed, it was washed with deionized water and filtered three times, and finally dried at 60°C to constant weight to obtain polydopamine-coated flower-like nano-zinc oxide, the SEM image of which is shown as follows: Figure 2 As shown in (b1) and (b2).

[0105] 3) 1 g of polydopamine-coated flower-shaped nano-zinc oxide was ultrasonically dispersed in 20 mL of anhydrous ethanol, and then 0.25 g of stearic acid was added and stirred at room temperature for 2 h. After the reaction was completed, it was washed with anhydrous ethanol and filtered three times, and finally dried at 60°C to constant weight to obtain hydrophobic polydopamine-coated flower-shaped nano-zinc oxide, the SEM image of which is shown as follows: Figure 2 As shown in (c1) and (c2).

[0106] Depend on Figure 2Comparison of (a1) and (a2) with (b1) and (b2) and (c1) and (c2) shows that flower-shaped nano-zinc oxide is indeed prepared in this embodiment, and the coating and hydrophobic modification of polydopamine do not cause obvious changes in its microstructure, and it still presents flower-shaped spherical micron-sized particles.

[0107] The above flower-like nano zinc oxide (ZnO), polydopamine-coated flower-like nano zinc oxide (ZnO@PDA), hydrophobic polydopamine-coated flower-like nano zinc oxide (ZnO@PDA@SA), XRD spectra are shown as follows Figure 3 As shown, the FTIR spectra of ZnO, SA, ZnO@PDA, and ZnO@PDA@SA are as follows Figure 4 The XPS spectra of ZnO@PDA and ZnO@PDA@SA are shown in Figure 5 shown.

[0108] Depend on Figure 3 From the XRD spectrum, it can be seen that 11 diffraction peaks at 31.7°, 34.4°, 36.2°, 47.5°, 56.5°, 62.8°, 66.5°, 67.9°, 69.0°, 72.5° and 76.9° correspond to the (100), (002), (101), (102), (110), (103), (200), (112), (201), (004) and (202) crystal planes of ZnO, respectively. It can be seen that PDA coating and SA modification have no effect on the crystal structure of ZnO.

[0109] Depend on Figure 4 It can be seen from the FTIR spectrum of ZnO@PDA that compared with the infrared spectrum of ZnO, the -1 、1494cm -1 and 1284cm -1 New peaks appeared at 3300 cm-1, indicating the presence of C=O, C=N and / or C=C, and CO bonds related to polydopamine. In addition, the hydroxyl peak shifted to 3300 cm-1. -1 The shift can be attributed to the introduction of -NH- groups in the polydopamine structure. This result shows that polydopamine (PDA) is successfully coated on the ZnO surface. For the stearic acid-modified polydopamine-coated zinc oxide particles (ZnO@PDA@SA), the high frequency region of about 2920 cm -1 and 2848cm -1 The absorption peaks at 1704 cm-1 are attributed to the asymmetric and symmetric stretching vibrations of the -CH2- group, respectively. -1 The peak at 2700~2900m is attributed to the disappearance of -COOH group in stearic acid due to the reaction to form zinc stearate. -1The characteristic peak of SA appeared at , indicating that SA successfully modified it.

[0110] Depend on Figure 5 In the XPS comparison of ZnO@PDA and ZnO@PDA@SA, the appearance of N element further confirms the successful coating of PDA.

[0111] 2. Preparation of mesoporous silica loaded with antifouling agent:

[0112] 1) 0.3 g of mesoporous silica (TEM image of which is shown in Figure 7 a1 and a2) were ultrasonically dispersed in 30 ml of anhydrous methanol, and the air in the pores was removed by vacuum;

[0113] 2) Then, 0.9 g of bromopyrrolecarbonitrile was added to the above solution, dissolved by ultrasonication, and the mixture was sealed and stirred for 24 h;

[0114] 3) After the stirring is completed, the mixture is washed with anhydrous ethanol and filtered three times. The product is dried at room temperature to a constant weight to obtain mesoporous silica loaded with an antifouling agent. The TEM image of the silica is shown in FIG. Figure 7 As shown in a3 and a4 of Figure 7 a5~a6.

[0115] The TG and FTIR curves of the above mesoporous silica and the mesoporous silica loaded with the antifouling agent Tra are as follows: Figure 6 As shown in (a) and (b), the TG results show that the loading amount of the antifouling agent Tra is about 5.71%. In the FTIR curve, 2250-2200 cm -1 (C≡N peak of Tra), 1450cm -1 (-CF3 stretching vibration peak of Tra), 785-540cm -1 (C-Cl stretching vibration peak of Tra) and 650-510cm -1 The appearance of the characteristic peak at (C-Br stretching vibration peak of Tra) proves that Tra is loaded in mesoporous silica.

[0116] Depend on Figure 7 From a1 and a2, we can see that mesoporous silica has a large number of mesoporous structures. Figure 7 As can be seen from a3 and a4, the surface mesopores of the mesoporous silica are blocked. The EDS results show that the characteristic elements of F, Cl, Br, and N are evenly distributed, proving the loading of the antifouling agent.

[0117] 3. Preparation of rough substrate:

[0118] 1) Dissolve 1 g of the polyurethane substrate prepared in Example 1 in 5 mL of anhydrous ethanol, spray an appropriate amount of the solution onto a Q235 carbon steel surface preheated at 60°C using a spray gun, and continue heating for 30 minutes;

[0119] 2) 0.2 g of the flower-like zinc oxide product obtained in Example 2 and 0.2 g of the antifouling agent-loaded mesoporous silica product prepared in Example 2 were ultrasonically dispersed in 5 mL and sprayed onto the surface of the above step 1) using a spray gun. The mixture was cured at room temperature for 24 h to obtain a rough substrate.

[0120] Example 3 - Construction of solid phase change lubricating layer

[0121] 1) 1 g of polyethylene wax and 9 g of tetradecane were heated and melted to mix;

[0122] 2) The mixed solution was dropped onto the preheated rough substrate surface obtained in Example 2, and after infiltration and cooling, an ultra-slip anti-fouling surface with photothermal self-repairing properties was obtained.

[0123] Example 4 - Construction of solid phase change lubricating layer

[0124] 1) 1.5 g of polyethylene wax and 8.5 g of tetradecane were heated and melted to mix;

[0125] 2) The mixed solution was dripped onto the preheated rough substrate surface obtained in Example 2 until the surface was completely wetted and covered. After cooling, an ultra-slip anti-fouling surface with photothermal self-repairing properties was obtained.

[0126] Example 5 - Construction of solid phase change lubricating layer

[0127] 1) 2 g of polyethylene wax and 8 g of tetradecane were heated and melted and mixed;

[0128] 2) The mixed solution was dropped onto the preheated rough substrate surface obtained in Example 2, and after infiltration and cooling, an ultra-slip anti-fouling surface with photothermal self-repairing properties was obtained.

[0129] Example 6 - Construction of solid phase change lubricating layer

[0130] 1) 3 g of polyethylene wax and 7 g of tetradecane were heated and melted and mixed;

[0131] 2) The mixed solution was dropped onto the preheated rough substrate surface obtained in Example 2, and after infiltration and cooling, an ultra-slip anti-fouling surface with photothermal self-repairing properties was obtained.

[0132] The water contact angle and sliding angle of the lubricating layer surface constructed by the above-mentioned different ratios of polyethylene wax and tetradecane are as follows: Figure 8 As shown in (a) and (b), it can be seen that when the content of tetradecane is 90% and 85%, it has better droplet dynamic wetting performance.

[0133] Figure 9 The state stability of the solid phase change lubricating layer at different proportions after heating, melting, mixing, cooling, inversion and shaking. It can be seen that the stability is poor when the content of tetradecane is 90% (the stable state fails after inversion and shaking), and the state is more stable when the content is 85% (it remains stable after inversion and shaking).

[0134] The present invention adopts near infrared light source (2w / cm 2 ) The ultra-smooth surface of Example 4 was irradiated at a distance of 10 cm, and the temperature change in the irradiated area was measured using a thermocouple. The obtained photothermal heating curve is shown as follows: Figure 10 As shown in (a); the ultra-smooth surface of Example 4 was artificially scratched with a scalpel, the surface was irradiated with a near-infrared light source, and the surface repair process was recorded by an optical microscope. The optical image of the photothermal repair was as shown in FIG. Figure 10 As shown in (b~d).

[0135] The present invention performs an antibacterial test on the super-slip surface obtained in Example 4 as a sample, and the test method is as follows:

[0136] BSA anti-adhesion test

[0137] The samples were immersed in 20 mL of 0.05 mg / mL FITC-labeled bovine serum albumin (FITC-BSA) solution and incubated at 30°C for 24 hours while shaking on a shaker at 120 rpm to simulate both static and dynamic environments. The samples were then observed and photographed using an inverted fluorescence microscope.

[0138] Anti-algae test

[0139] The samples were placed in f / 2 culture medium with Chlorella and incubated at 23°C day and night. The samples were then placed under an optical microscope to observe the attachment of Chlorella to the sample surface.

[0140] Antibacterial testing

[0141] The Luria-Bertani (LB) plate method was used to study the antibacterial properties of the samples (including the blank glass sample and the super-slip antifouling surface sample obtained in Example 4) against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). First, the bacteria were cultured in LB medium for 24 hours to obtain a concentration of 10 8 CFU / mL of bacterial suspension.

[0142] The samples were immersed in 20 mL bacterial suspension and incubated for 24 h at 30 °C under static and dynamic conditions, respectively. After removing the samples, they were gently rinsed with sterile phosphate buffer solution (PBS) to remove weakly attached bacteria; then the samples were placed in 20 mL sterile PBS and sonicated for 15 min. Finally, the liquid after sonication was diluted 10000 times and inoculated on LB medium and incubated at 30 °C for 24 h, and the antibacterial performance of the samples was evaluated by observing the colony formation on the LB medium.

[0143] Pseudomonas sp. (P. sp.) was selected as the marine model bacteria. The sterilized samples were incubated in P. sp. liquid in a 30 °C constant temperature incubator (static condition) and a constant temperature oscillation incubator (simulated dynamic condition), respectively. After soaking in P. sp. culture medium for 7, 14 and 28 days, the samples were rinsed with sterile PBS buffer to remove planktonic bacteria, then stained with 0.2 wt% crystal violet solution for 15 min, and rinsed with PBS buffer for 3 times. Then, the stained biofilm was observed using an optical microscope.

[0144] The test results are shown in Table 1. Figure 11 As can be seen from Table 1, the super-slippery surface shows excellent antifouling performance for bovine serum albumin, Escherichia coli, Staphylococcus aureus, Chlorella vulgaris and Pseudomonas sp.

[0145] The above description of disclosed embodiments enables one skilled in the art to make or use the application. Numerous modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein can be applied to other embodiments without departing from the spirit or scope of the application. Therefore, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. An ultra-slip anti-fouling surface with photothermal self-repairing properties, characterized in that: comprising a photoresponsive substrate and a lubricating layer formed on the photoresponsive substrate; The raw materials for preparing the lubricating layer include polyethylene wax and C12-C16 alkanes.

2. The ultra-slip anti-fouling surface according to claim 1, characterized in that The mass ratio of the polyethylene wax to the C12-C16 alkane is (1-3):

9.

3. The ultra-slip anti-fouling surface according to claim 1 or 2, characterized in that: The C12-C16 alkane includes any one of dodecane, tetradecane or hexadecane.

4. The ultra-slip antifouling surface according to any one of claims 1 to 3, characterized in that The photoresponsive substrate comprises a substrate body and a functional auxiliary agent layer formed on the substrate body; The raw materials for preparing the functional auxiliary agent layer include an antibacterial agent coated with a light-responsive substance and a mesoporous material loaded with an antifouling agent.

5. The ultra-slip anti-fouling surface according to claim 4, characterized in that The antibacterial agent coated with the light-responsive substance is hydrophobically modified; The hydrophobic agent used for the hydrophobic modification is selected from any one or more of stearic acid, perfluorodecyltrimethoxysilane or γ-aminopropyltriethoxysilane.

6. The ultra-slip anti-fouling surface according to claim 4 or 5, characterized in that: The substrate body includes any one or more of polyurethane, epoxy resin or polyurea; The light-responsive substance is formed by polymerization of dopamine hydrochloride and tris(hydroxymethyl)aminomethane on the surface of the antibacterial agent; The antibacterial agent includes any one or more of zinc oxide, flower-shaped zinc oxide or spherical zinc oxide; The antifouling agent includes any one or more of bromopyrrole nitrile, chitosan quaternary ammonium salt or benzisothiazolinone; The mesoporous material includes any one or more of mesoporous silica, hollow mesoporous silica or mesoporous silica.

7. A method for preparing an ultra-slip and anti-fouling surface according to any one of claims 1 to 6, characterized in that: The following steps are involved: S1: Provide photoresponsive substrate; S2: heating and melting polyethylene wax and C12-C16 alkanes and mixing them, contacting the mixture with the surface of the photoresponsive substrate in step S1, and cooling the mixture to obtain an ultra-slip and anti-fouling surface.

8. The preparation method according to claim 7, characterized in that The photoresponsive substrate was prepared according to the following method: (1) coating the substrate bulk solution on the preheated carrier surface and heating it to a semi-cured state; (2) mixing the antibacterial agent coated with the photoresponsive substance and the mesoporous material loaded with the antifouling agent with a solvent to obtain a mixed solution, introducing the mixed solution into the semi-cured product obtained in step (1), and curing the mixed solution to obtain a photoresponsive substrate; The light-responsive substance is formed by polymerization of dopamine hydrochloride and tris(hydroxymethyl)aminomethane on the surface of the antibacterial agent.

9. The preparation method according to claim 8, characterized in that The mass ratio of dopamine hydrochloride, tris(hydroxymethyl)aminomethane and antibacterial agent is (2-3):(1-1.5):(1-1.5); The mass ratio of the antifouling agent to the mesoporous material is (2-4):(1-1.5); The photoresponsive substance-coated antibacterial agent is a photoresponsive substance-coated antibacterial agent modified by a hydrophobic agent; the mass ratio of the hydrophobic agent, dopamine hydrochloride, tris(hydroxymethyl)aminomethane and antibacterial agent is (0.5-1):(2-3):(1-1.5):(1-1.5).

10. Use of the ultra-slippery antifouling surface according to any one of claims 1 to 6 or the ultra-slippery antifouling surface prepared by the preparation method according to any one of claims 7 to 9 in the field of anti-marine biofouling.

Images