Photo-thermal super-hydrophobic composite multilayer film based on bionic sea urchin structure and preparation method and application of photo-thermal super-hydrophobic composite multilayer film

Abstract

The invention discloses a photo-thermal super-hydrophobic composite multilayer film based on a bionic sea urchin structure and a preparation method and application thereof, and belongs to the technical field of functional materials. According to the photo-thermal super-hydrophobic composite multilayer film based on the bionic sea urchin structure, a copper oxide transition layer, a titanium nitride photo-thermal layer and a super-hydrophobic copper oxide outer layer are sequentially arranged on the surface of a base material from bottom to top; the copper oxide transition layer is located on the base material and is of a needle-shaped structure; the titanium nitride photo-thermal layer is located on the surface of the copper oxide transition layer and is of a spherical structure; the super-hydrophobic copper oxide outer layer is located on the spherical structure of the titanium nitride photo-thermal layer and is of an urchin-shaped nanoneedle structure. The photo-thermal super-hydrophobic composite multilayer film based on the bionic sea urchin structure is applied to the fields of surface protection, solar driven hydrophobic anti-icing, surface self-cleaning and the like, the anti-icing and deicing capacity can be effectively improved, and the protection effect is achieved with lower cost and better effect.

Description

Technical Field

[0001] The present invention belongs to the technical field of functional materials, and particularly relates to a photothermal superhydrophobic composite multi-layer film based on a bionic sea urchin structure, a preparation method thereof, and an application thereof. Background Art

[0002] Disclosing the information of this background art section is only intended to enhance the overall understanding of the present invention, and it is not necessarily regarded as an admission or an implication in any form that this information constitutes the prior art already known to those of ordinary skill in the art.

[0003] Large-area ice and snow accumulation may cause power line breakage, building collapse, seriously endanger traffic, and cause huge social losses. In industrial production and other fields, key parts such as aircraft wings and engine inlets are prone to icing, which destroys flight stability. Icing on wind turbine blades increases additional loads and vibrations and significantly reduces power generation. With the development of economic construction, people have made great efforts in anti-icing and de-icing. Traditional anti-icing mostly relies on active anti-icing with external forces or energy, such as hot air, electric heating, and mechanical anti-icing. These methods have problems such as high cost, high energy consumption, low efficiency, and even environmental pollution, which do not conform to the concept of green development. People have developed a series of anti-icing strategies, such as photothermal materials, electrothermal materials, etc. Among them, superhydrophobic coatings with photothermal effects have received extensive attention. The superhydrophobicity of the coating reduces the ice nucleation sites and significantly slows down the ice formation rate. The photothermal conversion performance enables the coating to absorb sunlight and convert it into heat, promoting the melting of the ice layer and further improving its anti-icing performance (Wu L, Liu P, Hua X, et al. Photothermal superhydrophobic membrane based on breath figure: Anti-icing and deicing[J]. Chemical Engineering Journal, 2024, 480: 147553).

[0004] In recent years, inspired by natural plants such as lotus leaves, superhydrophobic surfaces have gradually come into people's sight. It is a special surface with a water contact angle (WCA) greater than 150° and a sliding angle (SA) less than 10°, and has a wide range of applications in self-cleaning, anti-corrosion, oil-water separation, fog water collection, etc. In addition, the unique micro-nano structure of the superhydrophobic surface has the ability to capture air and form an air layer, which can bounce back the impacting or condensing water droplets before icing, thus greatly extending the icing time and having excellent passive anti-icing ability (He H, Huang W, Guo Z. Superhydrophobic and photothermal SiC / TiN durable composite coatings for passive anti-icing / active de-icing and de-frosting[J]. Materials Today Physics, 2023, 30: 100927). Researchers have used various methods to enhance the mechanical strength of superhydrophobic surfaces, such as combining heat treatment and spraying treatment methods to prepare superhydrophobic thin films, effectively improving the mechanochemical robustness and stability of superhydrophobic thin films (Zhu T, Cheng Y, Huang J, et al. A transparent superhydrophobic coating with mechanochemical robustness for anti-icing, photocatalysis and self-cleaning[J]. Chemical Engineering Journal, 2020, 399: 125746). However, the rough structure of the superhydrophobic surface is likely to allow liquid droplets to penetrate into the surface structure in high humidity or low pressure environments, which is undoubtedly fatal to the surface structure, will destroy the superhydrophobicity of the surface, and cause the surface to lose its anti-icing ability (Chu F, Hu Z, Feng Y, et al. Advanced anti‐icing strategies and technologies by macrostructured photothermal storage superhydrophobic surfaces[J]. Advanced Materials, 2024, 36(31): 2402897). Therefore, traditional superhydrophobic surfaces with a single liquid-repellent property cannot meet the rapid requirements, and reasonably constructing a multi-layer surface helps to improve the anti-icing performance of the surface.

[0005] In the field of photothermal thin films, titanium nitride thin films are favored due to their excellent photothermal properties. The thin film composed of titanium nitride nanoparticles is a photothermal material with plasmonic effects, which can convert light energy into heat energy and dissipate it. Researchers embedded titanium nitride particles into the metal surface with micro / nanostructures, such as aluminum, and finally obtained a photoselective photothermal superhydrophobic thin film, which exhibited excellent anti-icing ability and could significantly improve solar energy collection and reduce heat radiation loss (Ma W, Li Y, Chao C Y H, et al. Solar-assisted icephobicity down to −60°C with superhydrophobic selective surfaces[J]. Cell Reports Physical Science, 2021, 2(3)).

[0006] In the aspect of bionic technology, some researchers were inspired by honeycombs and cactus spines to prepare the MAHC (Microspine Array with Honeycomb and Cactus-Inspired Structures) structure for developing surface materials with special properties. This structure was developed through a laser layer-by-layer microfabrication strategy and had excellent mechanical durability and anti-icing hydrophobic properties (Zhou M, Zhang L, Zhong L, et al. Robust photothermal icephobic surface with mechanical durability of multi-bioinspired structures[J]. Advanced Materials, 2024, 36(3): 2305322), but this method had expensive equipment and high costs and was difficult to scale up. Summary of the Invention

[0007] Aiming at the problems existing in the prior art, the present invention provides a photothermal superhydrophobic composite multi-layer thin film based on a bionic sea urchin structure, a preparation method and an application thereof, which are applied to fields such as surface protection, solar-driven hydrophobic anti-icing, and self-cleaning surfaces, and can effectively improve the anti-icing and de-icing ability and play a protective role with lower cost and better effect.

[0008] The present invention is realized through the following technical solutions: A photothermal superhydrophobic composite multi-layer thin film based on a bionic sea urchin structure is sequentially provided with a copper oxide transition layer, a titanium nitride photothermal layer, and a superhydrophobic copper oxide outer layer from bottom to top on the substrate surface; The copper oxide transition layer is located on the substrate and has a needle-like structure; The titanium nitride photothermal layer is located on the surface of the copper oxide transition layer and has a spherical structure; The superhydrophobic copper oxide outer layer is located on the spherical structure of the titanium nitride photothermal layer and has a sea urchin-like nanostructure.

[0009] Furthermore, the thickness of the photothermal superhydrophobic composite multi-layer film based on the bionic sea urchin structure is 10 - 14.7 μm; among them, the thickness of the copper oxide transition layer is 8 - 12.5 μm, the thickness of the titanium nitride photothermal layer is 500 - 1000 nm, and the thickness of the superhydrophobic copper oxide outer layer is 600 - 1200 nm.

[0010] Furthermore, the copper oxide in the copper oxide transition layer and the outermost copper oxide layer contains a mixed phase of Cu(OH)2 and CuO.

[0011] Furthermore, the substrate is a ceramic, glass or metal matrix whose surface needs anti-icing.

[0012] In the present invention, a preparation method of the photothermal superhydrophobic composite multi-layer film based on the bionic sea urchin structure is also disclosed, which includes the following steps: (1) Using magnetron sputtering technology, a bottom copper film is prepared on the surface of the substrate. After preparation, the bottom copper film is immersed in a mixed solution of sodium hydroxide and ammonium persulfate for oxidation treatment to obtain a copper oxide transition layer; (2) Using magnetron sputtering technology to sputter titanium nitride on the surface of the copper oxide transition layer to form a titanium nitride photothermal layer; (3) Using magnetron sputtering technology to prepare a surface copper film on the titanium nitride photothermal layer, and then immersing it in a mixed solution of sodium hydroxide and ammonium persulfate for oxidation treatment; (4) Performing superhydrophobic treatment on the oxidized film to obtain a superhydrophobic copper oxide outer layer, and finally obtaining a photothermal superhydrophobic film with a sea urchin-like microstructure.

[0013] Further, the operating conditions of the magnetron sputtering technology in step (1) are as follows: the argon flow rate is 30 SCCM, the substrate is cleaned under the conditions of a bias voltage set at -600 V, a frequency of 40 kHz, a duty cycle of 75%, and a gas atmosphere of 3.0 Pa; the target is cleaned using a DC power supply with a set power of 160 W under an atmosphere of 0.5 Pa; the substrate bias parameter is set to a negative bias voltage of -50 V, a frequency of 40 kHz, and a duty cycle of 75%, and the bottom copper film is prepared using a DC power supply with a set power of 160 W under an atmosphere of 0.5 Pa, and the coating time is 15 - 60 min; the operating conditions of the magnetron sputtering technology in step (2) are as follows: the argon flow rate is 30 SCCM, the substrate is cleaned under the conditions of a bias voltage set at -600 V, a frequency of 40 kHz, a duty cycle of 75%, and a gas atmosphere of 3.0 Pa. The target is cleaned using a DC power supply with a set power of 160 W under an atmosphere of 0.5 Pa; the nitrogen flow rate is set to 2 SCCM, the substrate bias parameter is set to a negative bias voltage of -50 V, a frequency of 40 kHz, and a duty cycle of 75%, and the titanium nitride layer is prepared using a DC power supply with a set power of 160 W under an atmosphere of 0.5 Pa, and the coating time is 2 h; the operating conditions of the magnetron sputtering technology in step (3) are as follows: the argon flow rate is 30 SCCM, the substrate is cleaned under the conditions of a bias voltage set at -600 V, a frequency of 40 kHz, a duty cycle of 75%, and a gas atmosphere of 3.0 Pa; the target is cleaned using a DC power supply with a set power of 60 W under an atmosphere of 0.5 Pa; the substrate bias parameter is set to a negative bias voltage of -50 V, a frequency of 40 kHz, and a duty cycle of 75%, and the surface copper is prepared using a DC power supply with a set power of 60 W under an atmosphere of 0.5 Pa, and the coating time is 3 min.

[0014] Further, in the mixed solution of sodium hydroxide and ammonium persulfate in step (2) and step (3), the concentration of sodium hydroxide is 3 mol / L, the concentration of ammonium persulfate is 0.13 ml / L, and the oxidation treatment time is more than eight minutes.

[0015] Further, the superhydrophobic treatment method in step (4) is as follows: 1H,1H,2H,2H - perfluorodecyltrimethoxysilane (PFTS) is used to perform fluorination treatment on the oxidized film in an oven atmosphere with a set temperature of 120 °C, and the fluorination treatment time is 100 - 140 min.

[0016] In the present invention, the prepared photothermal superhydrophobic composite multi - layer film based on the bionic sea urchin structure can be applied to de - icing materials or anti - icing materials.

[0017] Based on the synergy of the sea urchin-like microstructure on the film surface for light trapping and hydrophobicity, as well as the combination of the photothermal properties of the TiN film and the multi-layer film structure. The underlying copper film shows a needle-like shape after growth and oxidation treatment. The TiN prepared by magnetron sputtering can in-situ grow into spherical TiN particles on the surface of the needle-like copper oxide. When the photon frequency of the incident light matches the natural frequency of the electrons on the surface of the TiN particles, the interaction with the electric field around the TiN particles will cause collective oscillation, namely the local surface plasmon resonance (LSPR) effect. The LSPR effect can enhance the absorption of incident photons. The absorbed energy generates electron-hole pairs through the non-radiative relaxation mechanism due to the Landau damping phenomenon. These high-energy electrons generated by the non-radiative plasmon decay are called hot carriers. They will undergo a relaxation process, transitioning from the excited state to the ground state, and ultimately converting light energy into heat energy. At the same time, after the surface copper film is oxidized and hydrophobized, the final microstructure of the film surface is sea urchin-like. This microstructure can not only increase the scattering frequency of the incident light and improve the light trapping rate, but also has the ability to capture air and form an air layer. There is an "air cushion" between the water droplet and the film, resulting in a small contact area between the liquid and the solid. Both the small contact area and the air layer will hinder the heat transfer from the droplet to the superhydrophobic surface, thus slowing down the freezing process. At the same time, this sea urchin-like structure has a high structural curvature. According to the Gibbs-Thomson effect, it will increase the chemical potential or vapor pressure at the concave curved interface, thereby increasing the nucleation barrier for solidification and suppressing ice nucleation to a very low temperature. Even after freezing, the sea urchin-like structure can synergistically combine light trapping and superhydrophobic properties, converting more light energy into heat and transferring it to the ice layer to accelerate the melting of the ice layer. At the same time, due to the superhydrophobic properties of this structure, the small ice surface contact area and the hydrophobic groups on the superhydrophobic surface can greatly reduce the van der Waals force and hydrogen bonds, thus reducing the adhesion between the ice and the surface, enabling the ice layer to slide off the film surface without complete melting. Finally, the combined action of the above multiple effects endows the film with both photothermal and superhydrophobic properties. This film is applied in fields such as surface protection, solar-driven hydrophobic anti-icing, and self-cleaning surfaces, which can effectively improve the anti-icing and de-icing capabilities and play a protective role with lower cost and better effect. The sea urchin-like microstructure composite film prepared by magnetron sputtering not only has a lower cost but also can synergistically enhance light trapping and hydrophobicity.

[0018] Compared with the prior art, the beneficial effects achieved by the present invention are as follows: (1) The present invention utilizes the bionic principle to prepare a photothermal superhydrophobic composite multi-layer film based on a bionic sea urchin structure. Its microscopic structure is similar to the spherical structure of sea urchin spines, which can enhance the photothermal and superhydrophobic properties of the surface, playing a better protective role; it can have better photothermal and hydrophobic properties, making full use of the synergy of light trapping and hydrophobicity, as well as the combination of the photothermal properties of the TiN film and the multi-layer film structure, which can effectively improve the anti-icing and active de-icing properties of the surface, realize the protective effect on specific surfaces, and can be applied to fields such as solar energy water drive and ice prevention, reducing the harm of freezing; and the preparation process is simpler and the cost is lower.

[0019] (2) Under the illumination of 1 W / cm², the surface temperature of the photothermal superhydrophobic composite multi-layer film based on the bionic sea urchin structure prepared by the method of the present invention rises from room temperature of 25 °C to 100 - 115 °C within 10 minutes, the water contact angle is 155 - 160°, the rolling angle is less than 2°. Under the illumination of 1 W / cm², it only takes 450 - 550 seconds to melt the ice completely frozen on the film surface, while the 304 stainless steel without the film coverage under the same conditions needs more than 1000 seconds to melt completely. Description of the Drawings

[0020] The specification drawings forming a part of the present invention are used to provide a further understanding of the present invention. The schematic embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation to the present invention.

[0021] Figure 1 It is a schematic diagram of the preparation process of the photothermal superhydrophobic composite multi-layer film based on the bionic sea urchin structure; Figure 2 It is the XPS spectra of the copper oxide transition layers prepared in Examples 1 - 4 as Figure 2 shown. In the figure, (a) is the XPS spectrum, and (b) is the high-resolution Cu 2p spectrum; Figure 3 It is the test result diagram of the contact angle and rolling angle of the photothermal superhydrophobic composite multi-layer film based on the bionic sea urchin structure in Examples 1 - 4; Figure 4 It is the test result diagram of the photothermal performance of the photothermal superhydrophobic composite multi-layer film based on the bionic sea urchin structure in Examples 1 - 4; Figure 5 It is the test result diagram of the de-icing performance of the photothermal superhydrophobic composite multi-layer film based on the bionic sea urchin structure in Examples 1 - 4; Figure 6 It is the SEM image of the photothermal superhydrophobic composite multi-layer film based on the bionic sea urchin structure in Example 3. Detailed Embodiments

[0022] It should be noted that the following detailed description is illustrative and aims to provide further explanation of the present invention. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the technical field to which the present invention belongs.

[0023] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit the exemplary embodiments according to the present invention. As used herein, unless the context clearly indicates otherwise, the singular forms are also intended to include the plural forms. In addition, it should be understood that when the terms "comprise" and / or "include" are used in this specification, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.

[0024] In order to enable those skilled in the art to more clearly understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below in conjunction with specific embodiments.

[0025] An embodiment of the present invention provides a photothermal superhydrophobic composite multi-layer film based on a bionic sea urchin structure, which is sequentially arranged from bottom to top as a material to be anti-iced treated as a substrate, a copper oxide transition layer, a titanium nitride photothermal layer, and a superhydrophobic copper oxide outer layer; the copper oxide transition layer is located on the substrate and has a needle-like structure; the titanium nitride photothermal layer is located on top of the copper oxide transition layer and has a spherical structure; the superhydrophobic copper oxide outer layer is located on the spherical structure of the titanium nitride photothermal layer and has a sea urchin-like nanoneedle structure.

[0026] In some embodiments, the thickness of the photothermal superhydrophobic composite multi-layer film based on the bionic sea urchin structure is 10-15 μm, the thickness of the copper oxide transition layer is 8-12.5 μm, the thickness of the titanium nitride photothermal layer is 500-1000 nm, and the thickness of the superhydrophobic copper oxide outer layer is 600-1200 nm; the copper oxide transition layer contains a mixed phase of Cu(OH)2 and CuO; the substrate is a ceramic, glass, or metal matrix whose surface needs to resist icing.

[0027] An embodiment of the present invention also provides a preparation method for the photothermal superhydrophobic composite multi-layer film based on the bionic sea urchin structure. Figure 1 As a schematic diagram of the preparation process of the photothermal superhydrophobic composite multi-layer film based on the bionic sea urchin structure, it can be seen from Figure 1 that it includes magnetron sputtering to deposit a bottom copper film on the substrate and performing an oxidation treatment - magnetron sputtering to deposit a titanium nitride (TiN) photothermal film - magnetron sputtering to deposit a top copper film and performing an oxidation and fluorination (superhydrophobic) treatment.

[0028] Now, the photothermal superhydrophobic composite multi-layer film and structure based on the bionic sea urchin structure of the present invention will be described in conjunction with specific embodiments.

[0029] Example 1 (1)Substrate pretreatment: The surface of 304 stainless steel was cleaned by ultrasonic waves and wiped with anhydrous ethanol and lint-free cloth. (2)Preparation of copper oxide transition layer: The bottom copper film was prepared by magnetron sputtering technology. The process parameters were as follows: the argon flow rate was 30 SCCM, the substrate was cleaned for 10 min under the conditions of a bias voltage of -600 V, a frequency of 40 kHz, a duty cycle of 75%, and a gas atmosphere of 3.0 Pa; the target was cleaned for 10 min under the atmosphere of 0.5 Pa with the power of the DC power supply set at 160 W; the substrate bias parameter was a negative bias of -50 V, the frequency was 40 kHz, the duty cycle was 75%, and the bottom copper film was prepared under the atmosphere of 0.5 Pa with the power of the DC power supply set at 160 W, and the coating time was 15 min; after preparation, the bottom copper film was immersed in a mixed solution of 3 mol / L sodium hydroxide and 0.13 mol / L ammonium persulfate for 10 min for oxidation treatment to obtain a copper oxide transition layer with a thickness of about 8 μm. (3)Preparation of titanium nitride photothermal layer: Titanium nitride was sputtered on the surface of the copper oxide transition layer by magnetron sputtering technology. The process parameters were as follows: the argon flow rate was 30 SCCM, the copper oxide transition layer was cleaned for 10 min under the conditions of a bias voltage of -600 V, a frequency of 40 kHz, a duty cycle of 75%, and a gas atmosphere of 3.0 Pa; the target was cleaned for 10 min under the atmosphere of 0.5 Pa with the power of the DC power supply set at 160 W; the nitrogen flow rate was set at 2 SCCM, the substrate bias parameter was a negative bias of -50 V, the frequency was 40 kHz, the duty cycle was 75%, and a titanium nitride photothermal layer with a thickness of about 800 nm was formed under the atmosphere of 0.5 Pa with the power of the DC power supply set at 160 W, and the coating time was 2 h. (4)The surface copper film was prepared on the titanium nitride photothermal layer by magnetron sputtering technology. The process parameters were as follows: the argon flow rate was 30 SCCM, the titanium nitride photothermal layer was cleaned for 10 min under the conditions of a bias voltage of -600 V, a frequency of 40 kHz, a duty cycle of 75%, and a gas atmosphere of 3.0 Pa; the target was cleaned for 10 min under the atmosphere of 0.5 Pa with the power of the DC power supply set at 60 W; the substrate bias parameter was a negative bias of -50 V, the frequency was 40 kHz, the duty cycle was 75%, and the surface copper was prepared under the atmosphere of 0.5 Pa with the power of the DC power supply set at 60 W, and the coating time was 3 min; it was immersed in a mixed solution of 3 mol / L sodium hydroxide and 0.13 mol / L ammonium persulfate for 10 min for oxidation treatment to become copper oxide. (5) The film after oxidation treatment is subjected to superhydrophobic treatment. 50 μL of 1H,1H,2H,2H-perfluorodecyltrimethoxysilane (PFTS) is used to perform fluorination treatment on the film for 2 h in an oven atmosphere at a set temperature of 120 °C. The amount of PFTS used increases with the increase of the total surface of the fluorinated sample to ensure sufficient fluorination, and a superhydrophobic copper oxide outer layer with a thickness of about 900 nm is prepared. Finally, a photothermal superhydrophobic film with a sea urchin-like microstructure is obtained, labeled as CuO@TiN / CuO-15.

[0030] Example 2 (1) Substrate pretreatment: The surface of 304 stainless steel is cleaned using ultrasonic waves and wiped with anhydrous ethanol and lint-free cloth. (2) Preparation of the copper oxide transition layer: The bottom copper film is prepared by magnetron sputtering technology. The process parameters are as follows: the argon flow rate is 30 SCCM, the substrate is cleaned for 10 min under the conditions of a bias voltage set at -600 V, a frequency of 40 kHz, a duty cycle of 75%, and a gas atmosphere of 3.0 Pa; the target is cleaned for 10 min using a DC power supply with a set power of 160 W in an atmosphere of 0.5 Pa; the substrate bias parameter is a negative bias of -50 V, a frequency of 40 kHz, a duty cycle of 75%, and the bottom copper film is prepared using a DC power supply with a set power of 160 W in an atmosphere of 0.5 Pa for 30 min; after preparation, the bottom copper film is immersed in a mixed solution of 3 mol / L sodium hydroxide and 0.13 mol / L ammonium persulfate for oxidation treatment for 10 min to obtain a copper oxide transition layer with a thickness of about 9 μm. (3) Preparation of the titanium nitride photothermal layer: Titanium nitride is sputtered on the surface of the copper oxide transition layer by magnetron sputtering technology. The process parameters are as follows: the argon flow rate is 30 SCCM, the copper oxide transition layer is cleaned for 10 min under the conditions of a bias voltage set at -600 V, a frequency of 40 kHz, a duty cycle of 75%, and a gas atmosphere of 3.0 Pa; the target is cleaned for 10 min using a DC power supply with a set power of 160 W in an atmosphere of 0.5 Pa; the nitrogen flow rate is set at 2 SCCM, the substrate bias parameter is a negative bias of -50 V, a frequency of 40 kHz, a duty cycle of 75%, and a titanium nitride photothermal layer with a thickness of about 800 nm is formed using a DC power supply with a set power of 160 W in an atmosphere of 0.5 Pa for 2 h. (4)The surface copper film was prepared on the titanium nitride photothermal layer by magnetron sputtering. The process parameters were as follows: the argon flow rate was 30 SCCM, the bias voltage was set at -600 V, the frequency was 40 kHz, the duty cycle was 75%, and the gas atmosphere was 3.0 Pa. The titanium nitride photothermal layer was cleaned for 10 min; the power was set at 60 W with a DC power supply, and the target was cleaned for 10 min in an atmosphere of 0.5 Pa; the substrate bias parameter was a negative bias of -50 V, the frequency was 40 kHz, the duty cycle was 75%, the power was set at 60 W with a DC power supply, and the surface copper was prepared in an atmosphere of 0.5 Pa for 3 min; it was soaked in a mixed solution of 3 mol / L sodium hydroxide and 0.13 mol / L ammonium persulfate for 10 min for oxidation treatment; (5)The superhydrophobic treatment was carried out on the oxidized film. 50 μL of 1H,1H,2H,2H-perfluorodecyltrimethoxysilane (PFTS) was used to perform fluorination treatment on the film for 2 h in an oven atmosphere at a set temperature of 120 °C, and a superhydrophobic copper oxide outer layer with a thickness of about 900 nm was obtained. Finally, a photothermal superhydrophobic film with a sea urchin-like microstructure was obtained, labeled as CuO@TiN / CuO-30.

[0031] Example 3 (1)Substrate pretreatment: The surface of 304 stainless steel was cleaned by ultrasonic waves and wiped with anhydrous ethanol and lint-free cloth. (2)Preparation of the copper oxide transition layer: The bottom copper film was prepared by magnetron sputtering. The process parameters were as follows: the argon flow rate was 30 SCCM, the bias voltage was set at -600 V, the frequency was 40 kHz, the duty cycle was 75%, and the gas atmosphere was 3.0 Pa. The substrate was cleaned for 10 min; the power was set at 160 W with a DC power supply, and the target was cleaned for 10 min in an atmosphere of 0.5 Pa; the substrate bias parameter was a negative bias of -50 V, the frequency was 40 kHz, the duty cycle was 75%, the power was set at 160 W with a DC power supply, and the bottom copper film was prepared in an atmosphere of 0.5 Pa for 45 min; after preparation, the bottom copper film was soaked in a mixed solution of 3 mol / L sodium hydroxide and 0.13 mol / L ammonium persulfate for 10 min for oxidation treatment to obtain a copper oxide transition layer with a thickness of about 10 μm; (3)Preparation of titanium nitride photothermal layer: Titanium nitride was sputtered on the surface of the copper oxide transition layer by magnetron sputtering technology. The process parameters were as follows: the argon flow rate was 30 SCCM, the bias voltage was set at -600 V, the frequency was 40 kHz, the duty cycle was 75%, and the substrate was cleaned for 10 min under the gas atmosphere of 3.0 Pa; the power was set at 160 W using a DC power supply, and the target was cleaned for 10 min under the atmosphere of 0.5 Pa; the nitrogen flow rate was set at 2 SCCM, the substrate bias parameter was a negative bias of -50 V, the frequency was 40 kHz, the duty cycle was 75%, and the power was set at 160 W using a DC power supply. A titanium nitride photothermal layer with a thickness of about 800 nm was formed under the atmosphere of 0.5 Pa, and the coating time was 2 h; (4)The surface copper film was prepared on the titanium nitride photothermal layer by magnetron sputtering technology. The process parameters were as follows: the argon flow rate was 30 SCCM, the bias voltage was set at -600 V, the frequency was 40 kHz, the duty cycle was 75%, and the titanium nitride photothermal layer was cleaned for 10 min under the gas atmosphere of 3.0 Pa; the power was set at 60 W using a DC power supply, and the target was cleaned for 10 min under the atmosphere of 0.5 Pa; the substrate bias parameter was a negative bias of -50 V, the frequency was 40 kHz, the duty cycle was 75%, and the power was set at 60 W using a DC power supply. The surface copper was prepared under the atmosphere of 0.5 Pa, and the coating time was 3 min; it was soaked in a mixed solution of 3 mol / L sodium hydroxide and 0.13 mol / L ammonium persulfate for 10 min for oxidation treatment; (5)The superhydrophobic treatment was carried out on the oxidized film. 50 μL of 1H,1H,2H,2H-perfluorodecyltrimethoxysilane (PFTS) was used to perform fluorination treatment on the film for 2 h under the oven atmosphere at a set temperature of 120 °C, and a superhydrophobic copper oxide outer layer with a thickness of about 900 nm was prepared. Finally, a photothermal superhydrophobic film with a sea urchin-like microstructure was obtained, labeled as CuO@TiN / CuO-45.

[0032] Example 4 (1)Substrate pretreatment: The surface of 304 stainless steel was cleaned by ultrasonic wave and wiped with anhydrous ethanol and lint-free cloth; (2)Preparation of copper oxide transition layer: The bottom copper film was prepared by magnetron sputtering technology. The process parameters were as follows: the argon flow rate was 30 SCCM, the substrate was cleaned for 10 min under the conditions of a bias voltage of -600 V, a frequency of 40 kHz, a duty cycle of 75%, and a gas atmosphere of 3.0 Pa; the target was cleaned for 10 min under the atmosphere of 0.5 Pa with the power of the DC power supply set at 160 W; the substrate bias parameter was a negative bias of -50 V, the frequency was 40 kHz, the duty cycle was 75%, and the bottom copper film was prepared under the atmosphere of 0.5 Pa with the power of the DC power supply set at 160 W for 60 min; after preparation, the bottom copper film was immersed in a mixed solution of 3 mol / L sodium hydroxide and 0.13 mol / L ammonium persulfate for oxidation treatment for ten minutes to obtain a copper oxide transition layer with a thickness of about 11 μm; (3)Preparation of titanium nitride photothermal layer: Titanium nitride was sputtered on the surface of the copper oxide transition layer by magnetron sputtering technology. The process parameters were as follows: the argon flow rate was 30 SCCM, the copper oxide transition layer was cleaned for 10 min under the conditions of a bias voltage of -600 V, a frequency of 40 kHz, a duty cycle of 75%, and a gas atmosphere of 3.0 Pa; the target was cleaned for 10 min under the atmosphere of 0.5 Pa with the power of the DC power supply set at 160 W; the nitrogen flow rate was set at 2 SCCM, the substrate bias parameter was a negative bias of -50 V, the frequency was 40 kHz, the duty cycle was 75%, and a titanium nitride photothermal layer with a thickness of about 800 nm was formed under the atmosphere of 0.5 Pa with the power of the DC power supply set at 160 W for 2 h; (4)The surface copper film was prepared on the titanium nitride photothermal layer by magnetron sputtering technology. The process parameters were as follows: the argon flow rate was 30 SCCM, the titanium nitride photothermal layer was cleaned for 10 min under the conditions of a bias voltage of -600 V, a frequency of 40 kHz, a duty cycle of 75%, and a gas atmosphere of 3.0 Pa; the target was cleaned for 10 min under the atmosphere of 0.5 Pa with the power of the DC power supply set at 60 W; the substrate bias parameter was a negative bias of -50 V, the frequency was 40 kHz, the duty cycle was 75%, and the surface copper was prepared under the atmosphere of 0.5 Pa with the power of the DC power supply set at 60 W for 3 min; it was immersed in a mixed solution of 3 mol / L sodium hydroxide and 0.13 mol / L ammonium persulfate for oxidation treatment for 10 min; (5)The oxidized film was subjected to superhydrophobic treatment. 50 μL of 1H,1H,2H,2H-perfluorodecyltrimethoxysilane (PFTS) was used to perform fluorination treatment on the film for 2 h in an oven atmosphere at a set temperature of 120 °C to obtain a superhydrophobic copper oxide outer layer with a thickness of about 900 nm, and finally a photothermal superhydrophobic film with a sea urchin-like microstructure was obtained, labeled as CuO@TiN / CuO-60.

[0033] Performance test The XPS spectra of the copper oxide transition layers prepared in Examples 1 to 4 are as follows Figure 2 shown. In the figure, (a) is the XPS spectrum and (b) is the high-resolution Cu 2p spectrum. The results show that the sample surface mainly contains four elements: Ti, Cu, O, and F. The Cu 2p spectrum proves that copper mainly exists in the form of CuO and partially exists in the form of Cu(OH)2.

[0034] The contact angles and rolling angles of the photothermal superhydrophobic films with sea urchin-like microstructures prepared in Examples 1 to 4 were tested, and the results are as follows Figure 3 shown. It can be seen from Figure 3 that the film contact angles of the photothermal superhydrophobic films with sea urchin-like microstructures are all greater than 155°, and the rolling angles are all less than 2°, showing excellent hydrophobic performance.

[0035] The photothermal properties of the photothermal superhydrophobic films with sea urchin-like microstructures prepared in Examples 1 to 4 were tested, and the results are as follows Figure 4 shown. The temperature increase curve of the photothermal superhydrophobic film with sea urchin-like microstructure under 1 W / cm² light irradiation for the same time. The temperature of this kind of film rises from room temperature of 25 °C to 100 - 115 °C within ten minutes. The results reflect that the composite film has excellent photothermal properties.

[0036] The deicing performance of the photothermal superhydrophobic films with sea urchin-like microstructures prepared in Examples 1 to 4 was tested, and the results are as follows Figure 5 shown. Under 1 W / cm² light irradiation, the film can melt the ice completely frozen on the surface in only 450 - 550 seconds. The 304 stainless steel without the film coverage under the same conditions needs more than 1000 seconds to completely melt.

[0037] The SEM image of the photothermal superhydrophobic film with sea urchin-like microstructure prepared in Example 3 is as follows Figure 6 shown. The results show that its microstructure is similar to that of a sea urchin, with a sea urchin-like needle-like structure.

Claims

1. A photothermal super-hydrophobic composite multilayer film based on a bionic sea urchin structure, characterized in that: A copper oxide transition layer, a titanium nitride photothermal layer and a super-hydrophobic copper oxide outer layer are sequentially arranged on the surface of the substrate from bottom to top; The copper oxide transition layer is located on the substrate and has a needle-like structure; The titanium nitride photothermal layer is located on the surface of the copper oxide transition layer and has a spherical structure; The super-hydrophobic copper oxide outer layer is located on the spherical structure of the titanium nitride photothermal layer and is a sea urchin-like nano-needle structure.

2. The photothermal super-hydrophobic composite multilayer film based on the bionic sea urchin structure according to claim 1, characterized in that: The thickness of the photothermal super-hydrophobic composite multilayer film based on the bionic sea urchin structure is 10-14.7 μm; wherein the thickness of the copper oxide transition layer is 8-12.5 μm, the thickness of the titanium nitride photothermal layer is 500-1000 nm, and the thickness of the super-hydrophobic copper oxide outer layer is 600-1200 nm.

3. The photothermal super-hydrophobic composite multilayer film based on the bionic sea urchin structure according to claim 2, characterized in that: The copper oxide in the copper oxide transition layer and the copper oxide outermost layer comprises a mixed phase of Cu(OH)2 and CuO.

4. The photothermal super-hydrophobic composite multilayer film based on the bionic sea urchin structure according to claim 1, characterized in that: The substrate is a ceramic, glass or metal substrate whose surface needs to be resistant to icing.

5. A method for preparing a photothermal super-hydrophobic composite multilayer film based on a bionic sea urchin structure according to any one of claims 1 to 4, characterized in that: The steps include: (1) Using magnetron sputtering technology, a bottom copper film is prepared on the surface of the substrate. After the preparation is completed, the bottom copper film is immersed in a mixed solution of sodium hydroxide and ammonium persulfate for oxidation treatment to obtain a copper oxide transition layer; (2) Using magnetron sputtering technology to sputter titanium nitride on the surface of the copper oxide transition layer to form a titanium nitride photothermal layer; (3) A surface copper film is prepared on the titanium nitride photothermal layer by magnetron sputtering technology, and then immersed in a mixed solution of sodium hydroxide and ammonium persulfate for oxidation treatment; (4) The oxidized film is subjected to a super-hydrophobic treatment to obtain a super-hydrophobic copper oxide outer layer, and finally a photothermal super-hydrophobic film with a sea urchin-like microstructure is obtained.

6. The method for preparing the photothermal super-hydrophobic composite multilayer film based on the bionic sea urchin structure according to claim 5, characterized in that: The operating conditions of the magnetron sputtering technology in step (1) are: argon gas flow rate 30 SCCM, the substrate is cleaned under the conditions of bias voltage set to -600 V, frequency of 40 kHz, duty cycle of 75%, and gas atmosphere of 3.0 Pa; The DC power supply was set to 160 W, and the target was cleaned in an atmosphere of 0.5 Pa. The substrate bias parameters were set to negative bias of -50 V, frequency of 40 kHz, and duty cycle of 75%. The DC power supply was set to 160 W, and the bottom copper film was prepared in an atmosphere of 0.5 Pa. The coating time was 15 to 60 min. The operating conditions of the magnetron sputtering technology in step (2) were: argon gas flow rate of 30 SCCM, the substrate was cleaned under the conditions of bias setting of -600 V, frequency of 40 kHz, duty cycle of 75%, and gas atmosphere of 3.0 Pa. The target material was cleaned in an atmosphere of 0.5 Pa by setting the power of a DC power supply to 160 W; the nitrogen flow rate was set to 2 SCCM, the substrate bias parameters were negative bias voltage -50 V, the frequency was 40 kHz, the duty cycle was 75%, and the power of a DC power supply was set to 160 W. The titanium nitride layer was prepared in an atmosphere of 0.5 Pa, and the coating time was 2 h; the operating conditions of the magnetron sputtering technology in step (3) were: the argon flow rate was 30 SCCM, the bias voltage was set to -600 V, the frequency was 40 kHz, the duty cycle was 75%, and the gas atmosphere was 3.0 Pa to clean the substrate; The DC power supply was set to 60 W, and the target was cleaned in an atmosphere of 0.5 Pa. The substrate bias parameters were set to a negative bias of -50 V, a frequency of 40 kHz, and a duty cycle of 75%. The DC power supply was set to 60 W, and the surface copper was prepared in an atmosphere of 0.5 Pa. The coating time was 3 min.

7. The method for preparing the photothermal super-hydrophobic composite multilayer film based on the bionic sea urchin structure according to claim 5, characterized in that: In the mixed solution of sodium hydroxide and ammonium persulfate in step (2) and step (3), the concentration of sodium hydroxide is 3 mol / L, the concentration of ammonium persulfate is 0.13 ml / L, and the oxidation treatment time is more than eight minutes.

8. The method for preparing the photothermal super-hydrophobic composite multilayer film based on the bionic sea urchin structure according to claim 5, characterized in that: The method for superhydrophobic treatment in step (4) is: using 1H,1H,2H,2H-perfluorodecyltrimethoxysilane (PFTS) to fluorinate the film after oxidation treatment in an oven atmosphere set at a temperature of 120°C, and the fluorination treatment time is 100~140 min.

9. Use of the photothermal super-hydrophobic composite multilayer film based on a bionic sea urchin structure as described in any one of claims 1 to 4 or the photothermal super-hydrophobic composite multilayer film based on a bionic sea urchin structure prepared by the preparation method as described in any one of claims 5 to 8 in deicing materials or anti-icing materials.

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