CN-122011845-A - Multifunctional super-hydrophobic coating based on in-situ grown nano titanium dioxide, and preparation method and application thereof

Abstract

The invention relates to the technical field of functional coatings, in particular to a multifunctional super-hydrophobic coating based on in-situ grown nano titanium dioxide, and a preparation method and application thereof. The super-hydrophobic coating consists of a coating matrix material and modified composite particles, wherein the coating matrix material is a high molecular polymer formed by multi-component polymerization, and the composite particles are carboxyl carbon nanotubes with titanium dioxide pellets grown on the surfaces in situ. The composite particles show spherical titanium dioxide grown on the carboxyl carbon nano tube structure in situ, and the perfluoro octyl triethoxysilane is adopted to carry out surface modification on the titanium dioxide, so that the surface energy is obviously reduced, the super-hydrophobic property of the coating is endowed, and the carboxyl carbon nano tube and the titanium dioxide pellets are combined with the coating matrix material through covalent bonds, so that the coating shows excellent wear resistance, corrosion resistance and ice resistance, and is particularly suitable for the fields of drag reduction, corrosion resistance and the like of marine ships.

Inventors

• MAN JIA
• LIU ZIHAO
• Ning Haohan
• ZHANG YONGQI
• SONG XINZHONG
• WANG SHEN
• LI JIANYONG
• JI MAOCHENG

Assignees

• 山东大学

Dates

Publication Date

20260512

Application Date

20260130

Claims (10)

1. 1. The multifunctional super-hydrophobic coating based on in-situ grown nano titanium dioxide is characterized by comprising a coating matrix material and modified composite particles; The coating matrix material is a high molecular polymer which is at least one selected from epoxy resin, fluorocarbon resin, fluorosilicone resin and polydimethylsiloxane; The composite particles are carboxyl carbon nanotubes with titanium dioxide grown on the surfaces in situ; The modifier is low surface energy silane selected from perfluorooctyl triethoxysilane or perfluorodecyl triethoxysilane.
2. 2. The superhydrophobic coating of claim 1, wherein the high molecular polymer is selected from the group consisting of fluorocarbon resins and polydimethylsiloxanes.
3. 3. The superhydrophobic coating of claim 2, wherein the mass ratio of fluorocarbon resin to polydimethylsiloxane is 3-5:1.
4. 4. The superhydrophobic coating of claim 1, wherein the carboxycarbon nanotubes have a length of 100-200 μm and the in-situ grown titanium dioxide has a particle size of 20-30 nm, or the mass ratio of modified composite particles to coating matrix material is 0.2-0.3:1.
5. 5. The method for preparing the superhydrophobic coating according to claim 1, comprising the steps of: (1) Dispersing the carboxyl carbon nano tube in ethanol water solution, adding glacial acetic acid solution and deionized water, performing ultrasonic dispersion, then adding tetrabutyl titanate, stirring for reaction, adding a modifier for reaction, and after the reaction is completed, cleaning, drying and grinding to obtain modified composite particles; (2) Adding a coating matrix material and a cross-linking agent into a diluting solvent, and then adding the modified composite particles prepared in the step (1), and carrying out ultrasonic treatment to uniformly disperse the modified composite particles; (3) And heating the substrate to a preset temperature, spraying a diluted solution containing modified composite particles and a coating matrix material on the surface of the substrate by adopting a spray gun under a preset pressure condition, and curing and drying the coating to obtain the super-hydrophobic coating.
6. 6. The method according to claim 5, wherein in the step (1), the ratio of the carboxyl carbon nanotubes to the tetrabutyl titanate is 1:1-3 g/mL; Or in the step (1), the dosage ratio of the carboxyl carbon nano tube to the ethanol water solution is 1:120-180 g/mL; Or in the step (1), the volume ratio of the glacial acetic acid solution to the deionized water is 1:0.9-1.1, and the volume ratio of the glacial acetic acid solution to the ethanol water solution is 1:12-18; Or, in the step (1), the ultrasonic time is 20-40 min; Or in the step (1), stirring reaction conditions are that stirring reaction is carried out at 20-30 ℃ for 2-4 h; Or, in the step (1), the dosage ratio of the modifier to the carboxyl carbon nano tube is 300-500:1 mu L/g; Or, in the step (1), adding the modifier and stirring for reaction for 10-15 h.
7. 7. The method of claim 5, wherein in step (2), the cross-linking agent is V-PDMS and N3390 curing agent; or, in the step (2), the diluting solvent is ethyl acetate; or in the step (2), the mass ratio of the coating matrix material to the cross-linking agent is 5-15:1; or in the step (2), the coating matrix material is fluorocarbon resin and polydimethyl vinyl siloxane, wherein the mass ratio of the fluorocarbon resin to the polydimethyl vinyl siloxane is 3-5:1; Or, in the step (2), the ultrasonic time is 20-40 min.
8. 8. The method according to claim 5, wherein in the step (3), the preset temperature is 45 to 60 ℃; Or, in the step (3), the preset pressure is 0.2-0.5M Pa; or, in the step (3), the drying condition is 150-200 ℃ and 10-30 min.
9. 9. Use of the superhydrophobic coating of any of claims 1-4 in the fields of underwater drag reduction, anti-icing, and corrosion protection.
10. 10. The use according to claim 9, wherein the superhydrophobic coating has a drag reduction of greater than 5% at reynolds numbers of 200-100000 in water or delays icing times as low as-15 ℃.

Description

Multifunctional super-hydrophobic coating based on in-situ grown nano titanium dioxide, and preparation method and application thereof Technical Field The invention relates to the technical field of functional coatings, in particular to a multifunctional super-hydrophobic coating based on in-situ grown nano titanium dioxide, and a preparation method and application thereof. Background The information disclosed in the background of the invention is only for enhancement of understanding of the general background of the invention and is not necessarily to be taken as an admission or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art. In the fields of ocean engineering and ships, the drag reduction technology is one of the core research directions for improving the sailing efficiency and reducing the operation energy consumption. When ships and marine equipment are sailed in a complex marine fluid environment, the surface roughness and friction resistance directly influence the overall performance and energy efficiency of the marine equipment. Although the traditional drag reduction coating can reduce the water flow resistance to a certain extent, the problems of insufficient wear resistance, shorter service life and the like are generally existed. In addition, the attachment of marine organisms to the hull surface can significantly increase drag, further resulting in reduced sailing efficiency. Therefore, the development of the high-performance coating which has excellent wear resistance and long-acting biological adhesion preventing capability and keeps stable drag reduction performance in a severe marine environment has important significance for improving the economy and sustainable operation of marine equipment. The super-hydrophobic coating can effectively prevent marine organism from adhering by virtue of the unique surface liquid-repellent characteristic and low surface energy, reduces resistance caused by biofouling, and has wide application potential in the field of marine drag reduction. However, the existing superhydrophobic coating still faces a plurality of challenges in a real marine environment, on one hand, the high-salt and high-humidity marine environment has extremely high requirements on the chemical and physical stability of the coating, the coating is easy to erode for a long time by seawater to deteriorate the performance, and on the other hand, the existing preparation process is difficult to realize the unification of mass production and stable performance of the coating. Therefore, the development of the super-hydrophobic coating with simple and convenient process, strong wear resistance and good environmental adaptability has important research value and application prospect for promoting the technical progress in the fields of ocean engineering and ships. Disclosure of Invention In view of the above, the invention provides a multifunctional super-hydrophobic coating based on in-situ grown nano titanium dioxide, and a preparation method and application thereof. The drag reduction rate of the coating in water under different Reynolds numbers is more than 5%, the icing time can be delayed under a low-temperature environment, and meanwhile, the coating has the effects of drag reduction and corrosion prevention, and has wide application prospects in the fields of ocean engineering, ship drag reduction and the like. In order to achieve the above object, the present invention is realized by the following technical scheme: In a first aspect, the invention provides a multifunctional superhydrophobic coating based on in-situ grown nano titanium dioxide, wherein the superhydrophobic coating consists of a coating matrix material and modified composite particles; The coating matrix material is a high molecular polymer; the composite particles are carboxyl carbon nanotubes with titanium dioxide grown on the surfaces in situ. The multifunctional super-hydrophobic coating based on the in-situ grown nano titanium dioxide plays a vital role, and can tightly and firmly anchor modified composite pipe particles on the surface of a substrate, so that a stable and continuous coating structure is formed. The composite particles have a unique tubular and spherical micro-nano composite structure and show a microstructure of long and small spheres (similar to grapes) with a rod-shaped structure, and the structural design not only endows the coating with extremely low surface energy, but also remarkably improves the contact angle with water, so that the coating shows excellent superhydrophobic performance, and a solid foundation is laid for the coating to exert excellent water resistance, drag reduction and other characteristics in various application scenes. Further, the high molecular polymer is at least one selected from epoxy resin, fluorocarbon resin, fluorosilicone resin and polydimethylsiloxane. Further, the high molecular polymer is s