Copper adhesive tape substrate light-heat super-hydrophobic anti-icing film layer and preparation method and application thereof

Abstract

The present application relates to the field of photothermal deicing technology, discloses a copper tape substrate photothermal super-hydrophobic deicing film layer and its preparation method and application, comprising: (1) forming a honeycomb structure on the surface of the copper foil of the conductive copper foil tape by laser etching technology to obtain a pretreated tape; (2) mixing alkali, reducing agent, water and selenium powder, then reacting, diluting with water to obtain a reaction solution, immersing the pretreated tape into the reaction solution for constant temperature reaction to obtain a super-hydrophilic H-Cu2Se substrate; (3) mixing polydimethylsiloxane, curing agent and dispersing agent to obtain a modified solution, immersing the super-hydrophilic H-Cu2Se substrate into the modified solution for dipping, and curing. The present application uses copper tape as a flexible substrate and copper source, constructs a narrow-bandgap semiconductor photothermal functional layer on the surface, and modifies it with PDMS to obtain a functional tape with excellent photothermal conversion performance, super-hydrophobicity, low ice adhesion and repeated use.

Description

Technical Field

[0001] This invention relates to the field of photothermal de-icing technology, specifically to a photothermal superhydrophobic de-icing film layer on a copper tape substrate, its preparation method, and its application. Background Technology

[0002] Low-temperature icing hazards widely endanger the safety of infrastructure such as power transmission lines, wind turbine blades, aircraft wings, and outdoor steel structures. They can easily cause line tripping, structural overload, equipment failure, and traffic disruptions, seriously threatening the stable operation of the power grid, aviation safety, and the long-term service life of outdoor engineering projects. Integrated surface technology combining passive superhydrophobic anti-icing and active solar thermal de-icing has become a mainstream research direction in the field of high-altitude outdoor anti-icing and de-icing. It relies on the surface's low wettability to delay water droplet freezing while utilizing in-situ solar thermal heating to melt accumulated ice, offering advantages such as green energy saving, no need for external power sources, and long-term protection.

[0003] Currently available photothermal superhydrophobic anti-icing coatings mostly employ spray-curing processes, requiring on-site application and lacking the ability to be repeatedly disassembled and transferred. They also exhibit poor adaptability to curved and irregularly shaped structures, and are prone to detachment and failure after repeated bending. Traditional photothermal functional materials often utilize graphene, carbon nanotubes, and precious metal nanoparticles, which suffer from cumbersome preparation processes, high raw material costs, poor bending stability, and weak interfacial adhesion. Some single selenide photothermal surfaces exhibit significant hydrophilic properties, failing to achieve long-term anti-icing effects. Conventional planar micro / nano structures have high ice adhesion and insufficient cyclic service durability, making it difficult to meet the engineering requirements for rapid deployment, repeated application, and flexible bending resistance under complex working conditions. Summary of the Invention

[0004] The purpose of this invention is to overcome the problems of existing anti-icing coatings, such as cumbersome construction, non-reusability, poor flexibility, easy failure upon bending, and insufficient synergy between photothermal and hydrophobic properties. This invention provides a photothermal superhydrophobic anti-icing film layer on a copper tape substrate, its preparation method, and its application. This invention uses a flexible copper tape as both a conductive substrate and a copper source. A biomimetic honeycomb micro-nano rough structure is constructed using laser structuring. An in-situ liquid-phase reduction selenization reaction is employed to grow a micro-flower-shaped Cu2Se high photothermal activity layer on the substrate surface. Then, PDMS low surface energy material is used for impregnation modification to control the wettability from superhydrophilic to stable superhydrophobic, ultimately resulting in a flexible, peelable, reusable, and ready-to-use composite anti-icing surface.

[0005] To achieve the above objectives, the present invention provides a method for preparing a photothermal superhydrophobic anti-icing film layer on a copper tape substrate, comprising: (1) A honeycomb structure is formed on the copper foil surface of the conductive copper foil tape using laser etching technology, and then the tape is cleaned and dried to obtain the pretreated tape. (2) After mixing alkali, reducing agent, water and selenium powder, a reaction is carried out to obtain selenium ion precursor solution. The selenium ion precursor solution is mixed with water to obtain a selenium-containing solution. Water is added to the selenium-containing solution to dilute it and a reaction solution is obtained. The pretreated tape is immersed in the reaction solution for a constant temperature reaction. Then the tape after the constant temperature reaction is washed and dried to obtain a superhydrophilic H-Cu2Se substrate. (3) Mix polydimethylsiloxane, curing agent and dispersant to obtain a modified liquid, immerse the superhydrophilic H-Cu2Se substrate in the modified liquid to obtain an impregnated substrate, and cure the impregnated substrate to obtain a copper tape substrate photothermal superhydrophobic anti-icing film layer.

[0006] Preferably, in step (1), the side length of the regular hexagonal unit in the honeycomb structure is 500-700 μm, and the distance between two adjacent regular hexagonal units is 50-70 μm.

[0007] Preferably, in step (2), the alkali is selected from sodium hydroxide and / or potassium hydroxide; The reducing agent is selected from sodium borohydride and / or potassium borohydride; The weight ratio of the alkali, reducing agent and selenium powder is 50-100:1-3:1.

[0008] Preferably, in step (2), the alkali, reducing agent, water and selenium powder are mixed and reacted, wherein the weight ratio of water to alkali is 1.5-2:1; The reaction time is 2-10 minutes.

[0009] Preferably, in step (2), the volume ratio of the selenium ion precursor solution to the selenium-containing solution is 1:3-5; The volume ratio of the selenium-containing solution to the reaction solution is 1:3-7.

[0010] Preferably, in step (2), the conditions for the isothermal reaction include: a temperature of 10-30°C and a time of 1-4 h.

[0011] Preferably, in step (3), the dispersant is selected from one or more of n-hexane, cyclohexane, and petroleum ether; The weight ratio of the polydimethylsiloxane to the curing agent is 8-12:1; The total content of polydimethylsiloxane and curing agent in the modified liquid is 1-15 wt%.

[0012] Preferably, in step (3), the impregnation conditions include: a temperature of 10-30°C and a time of 5-1800s; The curing conditions include a temperature of 60-80℃ and a time of 2-8 hours.

[0013] The second aspect of the present invention provides a photothermal superhydrophobic anti-icing film layer for a copper tape substrate prepared by the above preparation method.

[0014] The third aspect of the present invention provides an application of the above-mentioned copper tape substrate photothermal superhydrophobic anti-icing and de-icing film layer in low-temperature outdoor anti-icing and photothermal de-icing.

[0015] This invention uses commercial copper tape as a flexible substrate and copper source, and constructs a narrow bandgap semiconductor Cu2Se photothermal functional layer on its surface through in-situ reaction. Then, it is modified by impregnation with polydimethylsiloxane (PDMS) modified liquid, and finally obtains a functional tape with excellent photothermal conversion performance, superhydrophobicity, low ice adhesion and can be repeatedly pasted and used.

[0016] The beneficial effects of this invention are: 1. The preparation process is mild and simple, requiring no complex equipment. The raw materials are inexpensive and readily available, resulting in low overall preparation costs and easy large-scale engineering application.

[0017] 2. The composite material has excellent superhydrophobic properties, with a high static contact angle and an extremely low roll-off angle, which can effectively delay the freezing and adhesion of water droplets at low temperatures.

[0018] 3. Cu2Se semiconductors have broad-spectrum solar light absorption characteristics and excellent photothermal conversion efficiency. They can be rapidly heated under standard solar irradiation, enabling efficient in-situ photothermal melting of ice.

[0019] 4. The material exhibits significant anti-icing effect under low-temperature conditions, and can greatly extend the time for water droplets to freeze completely at -15 ℃, demonstrating outstanding passive anti-icing effect.

[0020] 5. The material has extremely low adhesion strength at the ice interface, and combined with the efficient photothermal effect, the ice layer can be quickly melted and detached under single solar irradiation in a low-temperature environment.

[0021] 6. Excellent substrate flexibility, supporting repeated bending, multiple peeling and transfer, and immediate application; adaptable to flat surfaces and various complex irregular curved surfaces; excellent durability during cyclic service. Attached Figure Description

[0022] Figure 1 This invention provides a process and working scenario diagram for preparing the photothermal superhydrophobic anti-icing film layer on a copper tape substrate. Figure 2 This is a scanning electron microscope image of the H-Cu2Se-PDMS surface from Example 1; Figure 3 This is the X-ray diffraction pattern of Cu2Se on the surface of the H-Cu2Se substrate in Example 1; Figure 4 These are comparison diagrams of the water contact angles on the surfaces of samples from Example 1 and Comparative Examples 1-2; Figure 5These are comparative images of the surface freezing process of samples from Example 1 and Comparative Examples 1-2; Figure 6 This is a quantitative comparison bar chart of delayed freezing time and ice adhesion strength on the surface of samples from Example 1 and Comparative Examples 1-2; Figure 7 This is a comparison of the temperature rise curves and photothermal melting time of the sample surfaces under one solar irradiation under Example 1 and Comparative Examples 1-2. Figure 8 These are images showing the results of repeatedly pasting the sample from Example 1 onto different planar substrates, including steel, copper, plastic, and glass. Figure 9 This is a comparison chart of the delayed freezing time of different substrate materials before and after the sample in Example 1 was pasted; Figure 10 This is a bar chart showing the changes in contact angle and roll angle of the sample in Example 1 after bending cycles at different radii of curvature. Figure 11 This is a graph showing the changes in delayed freezing time and photothermal melting time of the sample in Example 1 after different number of bending cycles. Detailed Implementation

[0023] The specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are for illustration and explanation only and are not intended to limit the present invention.

[0024] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0025] It should be noted that if the embodiments of the present invention involve directional indicators (such as up, down, left, right, front, back, etc.), the directional indicators are only used to explain the relative positional relationship and movement of the components in a certain specific posture (as shown in the figure). If the specific posture changes, the directional indicators will also change accordingly.

[0026] Furthermore, the technical solutions provided in the various embodiments of the present invention can be combined with each other, but only if they are feasible to those skilled in the art. If the combination of technical solutions is contradictory or cannot be implemented, it should be considered that such combination of technical solutions does not exist and is not within the scope of protection claimed by the present invention.

[0027] The present invention provides, in one aspect, a method such as Figure 1The method for preparing the photothermal superhydrophobic anti-icing film layer on the copper tape substrate shown in Figure a includes: (1) A honeycomb structure is formed on the copper foil surface of the conductive copper foil tape using laser etching technology, and then the tape is cleaned and dried to obtain the pretreated tape. (2) After mixing alkali, reducing agent, water and selenium powder, a reaction is carried out to obtain selenium ion precursor solution. The selenium ion precursor solution is mixed with water to obtain a selenium-containing solution. Water is added to the selenium-containing solution to dilute it and a reaction solution is obtained. The pretreated tape is immersed in the reaction solution for a constant temperature reaction. Then the tape after the constant temperature reaction is washed and dried to obtain a superhydrophilic H-Cu2Se substrate. (3) Mix polydimethylsiloxane, curing agent and dispersant to obtain a modified liquid, immerse the superhydrophilic H-Cu2Se substrate in the modified liquid to obtain an impregnated substrate, and cure the impregnated substrate to obtain a copper tape substrate photothermal superhydrophobic anti-icing film layer.

[0028] The conductive copper foil tape of the present invention serves as a substrate and a copper source. It includes a copper foil, on which an adhesive layer and a release paper are sequentially covered. During the preparation process of the present invention, the release paper is not removed. Thus, after obtaining the photothermal superhydrophobic anti-icing film layer of the copper tape substrate, the release paper can still be peeled off and the tape can still be properly adhered. Therefore, the adhesion is not lost under the preparation conditions of the present invention.

[0029] Furthermore, the conductive copper foil tape of the present invention is a flexible conductive copper foil tape with a minimum bending radius of 0.5-3mm and a total thickness of 20-35μm for the copper foil and the backing adhesive layer, which can meet the requirements for static bending and curved surface adhesion.

[0030] In one specific embodiment of the present invention, the conductive copper foil tape used has a specification of 30×30×0.02 mm. 3 (The thickness mentioned does not include the thickness of the release paper; the total thickness of the copper foil, adhesive layer, and release paper is 0.05 mm).

[0031] In step (1) of this invention, a honeycomb structure can be formed on the surface of copper foil by laser etching using a laser marking machine: first, draw the honeycomb pattern in the software, then scan with a laser along the set path to burn off part of the copper layer, and finally leave the honeycomb structure to construct the honeycomb micro-rough morphology; the main function of the honeycomb structure is to increase the durability of the sample.

[0032] In the preferred embodiment, in step (1), the side length of the regular hexagonal unit in the honeycomb structure is 500-700 μm, and the distance between two adjacent regular hexagonal units is 50-70 μm. The barrier of the honeycomb structure can resist wear, thereby maintaining superhydrophobic stability. The size of the honeycomb structure is controlled within this range in order to achieve the optimal balance between mechanical durability and low adhesion superhydrophobicity. The process parameters of the laser etching technology are: power of 15-19 W, frequency of 20-50 KHZ, and number of scans of 1-3.

[0033] In a specific implementation, the cleaning process in step (1) includes: first, ultrasonic cleaning with acetone for 5 minutes, then ultrasonic cleaning with anhydrous ethanol for 5 minutes, and finally ultrasonic cleaning with distilled water for 5 minutes; the purpose of this cleaning is to remove surface grease and contaminants. After cleaning, air dry or blow dry with nitrogen for later use.

[0034] Preferably, in step (2), the alkali is selected from sodium hydroxide and / or potassium hydroxide; the reducing agent is selected from sodium borohydride and / or potassium borohydride.

[0035] More preferably, in step (2), the weight ratio of the alkali, reducing agent and selenium powder is 50-100:1-3:1.

[0036] In step (2), the alkali, reducing agent, water and selenium powder are mixed and reacted, wherein the weight ratio of water to alkali is 1.5-2:1.

[0037] In step (2) of this invention, Cu2Se thin films are synthesized in situ on the surface of copper tape using a liquid-phase chemical method. Specifically, an alkaline reducing system is prepared by first mixing and stirring the alkali, reducing agent, and water until completely dissolved. Then, selenium powder is added and quickly dissolved. The mixture is stirred and reacted at room temperature for 2-10 minutes until the solution turns a stable reddish-brown color, indicating the formation of Se2Se. 2- Ions were obtained to produce a selenium ion precursor solution.

[0038] Further, the selenium ion precursor solution is mixed with water and stirred for 5 minutes to obtain a selenium-containing solution; preferably, the volume ratio of the selenium ion precursor solution to the selenium-containing solution is 1:3-5.

[0039] In this invention, room temperature refers to 20-30°C.

[0040] In this invention, diluting the selenium-containing solution with water reduces the ion concentration and reaction rate of the system, thereby slowing down the Cu₂Se deposition process and preventing vigorous reactions that could lead to film coarsening or agglomeration. This promotes the uniform growth of nanosheets and microflower structures. Under initial conditions of low water content, a higher local concentration of alkali and reducing agent can be maintained, thus promoting the rapid reduction of Se powder and the generation of active Se. 2-Species; if a large amount of water is added directly at the beginning, it will lead to a decrease in the alkalinity and reducing agent concentration of the system, which is not conducive to the activation and dissolution of Se powder. Preferably, in step (2), the volume ratio of the selenium-containing solution to the reaction solution is 1:3-7.

[0041] In this invention, in step (2), the amount of reaction solution used is sufficient to completely immerse the pretreated tape and ensure that the reaction solution completely covers the copper surface.

[0042] In a preferred embodiment, the conditions for the isothermal reaction in step (2) include: a temperature of 10-30°C and a time of 1-4 hours; during the isothermal reaction, the copper on the surface of the tape is oxidized to Cu. + , with Se in solution 2- By combining, a black, uniform Cu2Se thin film with a micro-flower structure is grown in situ on the copper surface.

[0043] In step (2), the tape after constant temperature reaction is rinsed several times with deionized water and ethanol alternately, and then placed in an oven at 50-80℃ to dry for 10-30 minutes to obtain a superhydrophilic H-Cu2Se substrate with micro-nano rough structure (H stands for "honey" honeycomb structure). Cu2Se is a narrow bandgap semiconductor with strong absorption capacity in a wide spectral range (especially the near-infrared region).

[0044] In step (3) of this invention, H-Cu2Se is modified with low surface energy by solution impregnation to give it superhydrophobicity.

[0045] Preferably, in step (3), the dispersant is selected from one or more of n-hexane, cyclohexane and petroleum ether; the curing agent is a curing agent used in conjunction with PDMS, purchased from Dow Corning, specifically brand name Dow Corning Sylgard 184, which is composed of hydrogen-containing silicone oil and platinum catalyst.

[0046] Further, in step (3), the weight ratio of polydimethylsiloxane (PDMS) to curing agent is 8-12:1; wherein the total content of polydimethylsiloxane and curing agent in the modified liquid is 1-15 wt%, and this concentration is one of the key parameters affecting the final hydrophobic performance.

[0047] Preferably, the amount of modified liquid used is sufficient to completely immerse the superhydrophilic H-Cu2Se substrate.

[0048] In step (3), the impregnation conditions include: temperature of 10-30℃ and time of 5-1800s. The impregnation time affects the degree of PDMS encapsulation and film thickness on the micro-nano structure, so the above range is more suitable.

[0049] Specifically, the total content of polydimethylsiloxane and curing agent in the modification solution, as well as the impregnation time, jointly determine the deposition thickness and uniformity of the modified layer on the micro / nano structure. Too low a concentration or too short a time may result in PDMS failing to completely cover the hydrophilic sites on the Cu2Se surface, leading to insufficient hydrophobicity and durability; too high a concentration or too long a time may over-fill the micro / nano structure, weakening its roughness and causing a decrease in superhydrophobicity. By optimizing these two parameters, the lowest surface energy modification can be achieved while maintaining micro / nano roughness, resulting in optimal superhydrophobic performance.

[0050] Preferably, the curing conditions in step (3) include: a temperature of 60-80℃ and a time of 2-8 h; under these conditions, PDMS is fully cross-linked and cured, firmly attached to the surface of the Cu2Se microflower structure, forming a stable superhydrophobic surface.

[0051] If PDMS modification is not used, the tape is superhydrophilic and will spread rapidly when water droplets are dropped onto the sample.

[0052] The second aspect of this invention provides a photothermal superhydrophobic anti-icing film layer on a copper tape substrate prepared by the above-mentioned method. The Cu2Se narrow bandgap semiconductor in the film possesses broad-spectrum solar light absorption capability and excellent photothermal conversion efficiency. The raw materials are readily available, and the preparation is mild and simple, with costs far lower than those of noble metal and carbon nanotube systems. The laser honeycomb microstructure and the low surface energy of PDMS synergistically construct a multi-level rough hydrophobic interface, significantly reducing the adhesion force between ice and the substrate. The flexible copper tape substrate can closely adhere to complex irregular surfaces such as planes, cylinders, wings, and blades, supporting multiple peeling and repeated pasting. Even after cyclic bending, it maintains a stable contact angle, low roll-off angle, and photothermal de-icing performance. The synergistic effect of multi-level honeycomb structure, efficient Cu2Se photothermal effect, and PDMS ultra-low surface energy gives the material excellent icing delay performance, rapid photothermal melting performance, low ice adhesion, flexibility and durability, bendability and reusability. It can be repeatedly peeled, conformally bonded and repeatedly transferred and pasted on the surfaces of planar copper sheets, steel, glass, cylindrical wires, wing models and wind turbine blade models. It has broad application prospects in the field of anti-icing of power, wind power and aviation equipment in high-altitude outdoor environments.

[0053] A third aspect of this invention provides an application of the aforementioned copper tape-based photothermal superhydrophobic anti-icing and de-icing film layer in low-temperature outdoor anti-icing and photothermal de-icing of power conductors, wind turbine blades, aerospace components, building structures, etc., such as... Figure 1 As shown in Figure b.

[0054] This invention uses commercially available copper tape as a base, which possesses excellent flexibility and adhesion. The in-situ grown honeycomb-microflower-like Cu2Se structure provides highly efficient photothermal conversion capabilities and micron-level roughness. PDMS modification not only provides low surface energy, but its inherent elastomer properties also protect the brittle Cu2Se microstructure during tape bending and application, enhancing overall durability. The combination of these three elements results in a final product that combines highly efficient photothermal de-icing, passive anti-icing (superhydrophobic delayed icing, low ice adhesion), and immediate application with mechanical flexibility.

[0055] Reusability and reusability: This characteristic stems directly from the commercially available copper tape substrate used. Its adhesive backing allows the tape to adhere firmly to various substrates (such as metal, glass, and plastic) and can be completely peeled off without damaging the functional layer (H-Cu2Se-PDMS). The strong bond between the functional layer and the tape substrate ensures that its photothermal and superhydrophobic properties do not significantly degrade during multiple peel-and-stick cycles.

[0056] In summary, this solution uses adhesive-backed conductive copper foil tape as a flexible substrate, enabling the coating to be self-adhesive, peelable, and transferable, eliminating the need for on-site spraying or curing and achieving rapid deployment. Furthermore, through the synergistic effect of a honeycomb microstructure, high photothermal conversion of Cu2Se, and superhydrophobicity of PDMS, it achieves long-lasting anti-icing, rapid photothermal de-icing, and low-icing adhesion, maintaining stable superhydrophobic properties and photothermal anti-icing and de-icing performance even after bending. These structural features and functional advantages work together to demonstrate significant application potential for this transferable, ready-to-use Cu2Se-PDMS composite coating in complex curved surfaces such as aircraft wings, blades, and power lines, as well as in on-site anti-icing and de-icing applications in engineering projects.

[0057] The present invention will be described in detail below through embodiments. Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods in the art. Unless otherwise specified, the experimental materials used in the following embodiments are commercially available.

[0058] In the following examples, room temperature refers to 25°C.

[0059] The conductive copper foil tape used in the following examples is a flexible conductive copper foil tape, which includes a copper foil, an adhesive layer and a release paper sequentially covered on the copper foil, with a minimum bending radius of 0.5 mm, a total thickness of 20 μm for the copper foil and the adhesive layer, and a total thickness of 0.05 mm for the copper foil, the adhesive layer and the release paper; the curing agent used is purchased from Dow Corning, brand name Dow Corning Sylgard 184.

[0060] Example 1 (1) Cut the conductive copper foil tape into 30×30×0.02 mm pieces. 3Size (this specification does not include the thickness of the release paper): A honeycomb structure is formed on the surface of the copper foil of the conductive copper foil tape using laser etching technology. The side length of the regular hexagonal unit in the honeycomb structure is 600μm, and the spacing between two adjacent regular hexagonal units is 60μm. The process parameters of the laser etching technology are: power of 19 W, frequency of 30 kHz, and scanning times of 1. Then, the tape is first ultrasonically cleaned with acetone for 5 min, then ultrasonically cleaned with anhydrous ethanol for 5 min, and finally ultrasonically cleaned with distilled water for 5 min. After drying, the pre-treated tape is obtained. (2) Add 1 g of alkali (sodium hydroxide) and 0.03 g of reducing agent (sodium borohydride) to 2 mL of deionized water and stir until completely dissolved (the weight ratio of deionized water to alkali is 2:1). Then quickly add 0.01 g of selenium powder and dissolve rapidly. Stir and react for 5 minutes at room temperature until the solution turns a stable reddish-brown color. The weight ratio of alkali, reducing agent, and selenium powder is 100:3:1. Mix the selenium ion precursor solution with 8 mL of deionized water and continue stirring for 5 minutes to obtain a selenium-containing solution. The volume ratio of the selenium ion precursor solution to the selenium-containing solution is 1:5 (the volume change of the solution is not considered when the solid dissolves). Dilute the selenium-containing solution with 40 mL of deionized water to obtain 50 g of selenium powder. mL of reaction solution, with a selenium-containing solution to reaction solution volume ratio of 1:5, the pretreated tape was completely immersed in the reaction solution and allowed to stand for constant temperature reaction. The constant temperature reaction conditions included: temperature of 25℃ and time of 1h. Then the tape after constant temperature reaction was washed three times alternately with deionized water and ethanol, and then dried in an oven at 60℃ for 30 minutes to obtain superhydrophilic H-Cu2Se substrate. (3) Mix polydimethylsiloxane and curing agent in a weight ratio of 10:1, then add dispersant (n-hexane) and mix. Stir magnetically for 2 hours to make the mixture uniform, and obtain a modified liquid. The total content of polydimethylsiloxane and curing agent in the modified liquid is 5 wt%. The superhydrophilic H-Cu2Se substrate is completely immersed in the modified liquid. The immersion conditions include: temperature of 25℃ and time of 2 minutes. The immersed substrate is then placed in an 80℃ oven for 2 hours to cure, and a copper tape substrate photothermal superhydrophobic anti-icing film layer is obtained, which is denoted as H-Cu2Se-PDMS.

[0061] The surface morphology of H-Cu2Se-PDMS was characterized using field emission scanning electron microscopy (FESEM), and the results are as follows: Figure 2 As shown, a micron-scale "flower cluster" structure composed of honeycomb walls was successfully constructed on the surface of the tape. This micro-nano hierarchical rough structure is the physical basis for achieving superhydrophobicity.

[0062] The Cu2Se phase on the surface of the superhydrophilic H-Cu2Se substrate obtained in step (2) was analyzed by X-ray diffraction, and the results are as follows: Figure 3As shown, all diffraction peaks match the standard card (JCPDS No. 06-0680) of β-Cu2Se, confirming the successful synthesis of the narrow bandgap semiconductor Cu2Se, which is the source of its efficient photothermal performance.

[0063] Example 2 The method of Example 1 was implemented, except that the total content of polydimethylsiloxane and curing agent in the modified liquid in step (3) was 2 wt%, and the immersion time was 5 seconds; a photothermal superhydrophobic anti-icing film layer of copper tape substrate was obtained, which was denoted as H-Cu2Se-PDMS-2.

[0064] Example 3 The method of Example 1 was implemented, except that the total content of polydimethylsiloxane and curing agent in the modified liquid in step (3) was 11 wt%, and the immersion time was 30 minutes; a photothermal superhydrophobic anti-icing film layer of copper tape substrate was obtained, which was denoted as H-Cu2Se-PDMS-3.

[0065] Comparative Example 1 The conductive copper foil tape of the same size as in Example 1, without any treatment, is designated as Cu-Tape.

[0066] Comparative Example 2 The method of Example 1 is implemented, except that the copper foil surface of the conductive copper foil tape is not laser etched in step (1), that is, the copper foil surface of the conductive copper foil tape does not form a honeycomb structure; a photothermal superhydrophobic anti-icing film layer of copper tape substrate is obtained, which is denoted as Cu2Se-PDMS.

[0067] Test Example 1 Characterization of surface wettability.

[0068] The water contact angle (WCA) of samples from Examples 1-3, Comparative Example 1, and Comparative Example 2 was measured using a contact angle meter. The results for Examples 1, Comparative Example 1, and Comparative Example 2 are as follows: Figure 4As shown, the H-Cu2Se-PDMS tape (Example 1) exhibits a water contact angle as high as 156.3°, demonstrating excellent superhydrophobicity and low adhesion properties. Comparative Example 1 (Cu-Tape) shows some hydrophilicity (WCA=83.9°), while Comparative Example 2 (Cu2Se-PDMS) also exhibits high hydrophobicity (WCA=152.5°). This comparison demonstrates that low surface energy modification with PDMS can impart high hydrophobicity to the Cu2Se surface, while the honeycomb-microflower composite structure further enhances hydrophobic stability, ice-delay effect, and low ice adhesion performance. The water contact angle of Example 2 is 132°. Analysis suggests that the low PDMS concentration and short impregnation time may have resulted in PDMS failing to fully penetrate and completely cover all hydrophilic sites of the micro / nano structure, thus failing to minimize surface energy and resulting in insufficient structural robustness. The initial water contact angle of Example 3 decreased to 135°, indicating a decline in hydrophobic properties. The presumed reason is that an excessively concentrated PDMS solution and a longer impregnation time may form a thicker polymer layer, partially filling the critical micro-nano gaps, and making it more prone to microcracks under repeated deformation. The results of Examples 2 and 3 confirm, from both positive and negative perspectives, that the PDMS concentration and impregnation time need to be synergistically optimized. The conditions in Example 1 are the optimal choice after system balancing, which can form a uniform, robust, and moderately thick low surface energy modification layer on the micro-nano structure, thereby achieving extreme superhydrophobicity while ensuring the overall mechanical robustness and functional durability of the tape.

[0069] Test Example 2 Passive anti-icing performance test.

[0070] The anti-icing performance of the surfaces of three samples (Example 1, Comparative Example 1, and Comparative Example 2) was tested in a climate chamber at -15 °C and 40 ± 5% relative humidity. The freezing process of a 10 μL water droplet on the sample surface was recorded using a high-speed camera. Figure 5 As shown in the figure, water droplets maintain high sphericity on both H-Cu2Se-PDMS and Cu2Se-PDMS surfaces, with H-Cu2Se-PDMS exhibiting a longer freezing delay time; while on the Cu-Tape surface, water droplets spread more significantly and freeze faster. Further quantitative analysis of the delayed freezing time for each sample, as well as the ice adhesion strength measured using a digital push-pull force gauge, was conducted. Figure 6As shown, H-Cu₂Se-PDMS exhibits a delayed freezing time of up to 1135 seconds and an ice adhesion strength as low as 2.64 kPa; Cu₂Se-PDMS has a delayed freezing time of 980 seconds and an ice adhesion strength of 4.58 kPa; Cu-Tape has a delayed freezing time of 86 seconds and an ice adhesion strength of 24.94 kPa. The test results for H-Cu₂Se-PDMS are significantly better than those for Cu-Tape and Cu₂Se-PDMS. This is attributed to its superhydrophobic surface energy, which greatly reduces the solid-liquid contact area, thus delaying heat conduction from the substrate to the water droplet and significantly weakening the mechanical interlocking effect of ice crystals on the rough structure.

[0071] Test Example 3 Photothermal conversion and active de-icing performance testing.

[0072] Using a xenon lamp to simulate sunlight (light intensity 100 mW cm⁻¹) -2 (i.e., one sun) irradiated the surfaces of the samples from Example 1, Comparative Example 1, and Comparative Example 2, and their temperature changes were monitored using an infrared thermal imager. The surface temperature rise curves of the three samples are shown below. Figure 7 As shown in Figure a, the equilibrium temperature of Cu2Se-PDMS is 74.3 ℃, the equilibrium temperature of Cu-Tape is 30.8 ℃, and H-Cu2Se-PDMS exhibits the highest equilibrium temperature (up to 79.5 ℃). This is attributed to the efficient photothermal conversion capability of the narrow bandgap semiconductor Cu2Se, as well as the multiple reflection and absorption enhancement effect (light trapping effect) generated by the honeycomb micro-flower structure.

[0073] At -15 °C, ice layers of uniform thickness were pre-placed on the surfaces of samples from Example 1, Comparative Example 1, and Comparative Example 2. The samples were then exposed to sunlight for one day, and the time required for the ice layers to completely melt was recorded. The results are as follows: Figure 7 As shown in Figure b, H-Cu₂Se-PDMS has the shortest photothermal de-icing time, requiring only 106 seconds, while Cu₂Se-PDMS takes 156 seconds, and Cu-Tape's photothermal de-icing time is significantly greater than 1800 seconds, demonstrating the superior active de-icing capability of H-Cu₂Se-PDMS. Its photothermal de-icing process involves the heat generated by photothermal conversion acting directly on the ice-tape interface through conduction, achieving rapid and low-energy ice removal.

[0074] Test Example 4 Verification of transferability, universality, and reusability.

[0075] The H-Cu2Se-PDMS tape prepared in Example 1 was completely peeled off from its release paper and then firmly adhered to four different flat substrates: steel plate, copper plate, plastic plate, and glass. The demonstration process is as follows: Figure 8As shown, the tape achieves conformal adhesion on all substrates without any edge lifting.

[0076] The delayed freezing time of each substrate surface before and after tape application was tested according to the method in Test Example 2. The results are as follows: Figure 9 As shown, after applying the tape, the anti-icing performance of all substrates was significantly and consistently improved, with the icing delay time being similar to that of the tape in independent tests. This fully demonstrates that the tape can effectively impart its photothermal superhydrophobic properties to various substrates, achieving universal applicability and solving the problem of poor compatibility between traditional coatings and substrates.

[0077] Test Example 5 Mechanical flexibility, durability and functional stability testing.

[0078] H-Cu2Se-PDMS tape was fixed on a programmable bending tester to simulate bending conditions in real-world applications. The tape was bent 1000 times at curvature radii of 1.5 mm, 1.0 mm, and 0.5 mm respectively to test its superhydrophobicity under different curvature radii. The results are as follows: Figure 10 As shown, the contact angle of the H-Cu2Se-PDMS tape remained above 150° and the roll-off angle below 10° under different radii of curvature, proving that its superhydrophobic properties did not significantly decrease under bending cycles. Then, repeated bending cycle tests were conducted at a curvature radius of 1.5 mm. After undergoing different numbers of bending cycles (e.g., 1000, 3000, 6000), the changes in delayed icing time and photothermal melting time were tested according to the methods in Test Example 2 and Test Example 3. The results are shown below. Figure 11 As shown, after 6000 bending cycles, the delayed icing time of the tape decreased from 1135 seconds to 817 seconds, and the defrosting time increased from 106 seconds to 403 seconds. This indicates that the material's performance degraded after severe bending cycles, but it still maintained good anti-icing and photothermal defrosting capabilities. This demonstrates that the flexible copper tape substrate, the tough PDMS encapsulation layer, and the robust in-situ growth interface together endow this functional tape with excellent mechanical durability, ensuring its long-term and reliable use on complex curved surfaces such as aircraft wings and wind turbine blades.

[0079] Based on the above embodiments and test results, this invention successfully prepared a multifunctional integrated smart tape by using commercial copper tape as a transferable substrate, in-situ growing narrow-bandgap semiconductor Cu2Se to construct a photothermal and micro-nano rough framework, and then modifying it with PDMS under optimized conditions for low surface energy. Its innovation and advantages are reflected in: (1) Functional synergy: Narrow-bandgap Cu2Se provides efficient photothermal conversion (active de-icing), which, combined with the superhydrophobicity (passive anti-icing) provided by the PDMS-modified micro-nano structure, achieves integrated anti-icing and de-icing; (2) Transferability and universality: Based on the tape form, it breaks the traditional binding relationship between coating and substrate, realizing the immediate use of functions and rapid deployment on substrates of different materials and shapes; (3) Robust and durable: In-situ growth ensures a firm bond between the functional layer and the substrate, and PDMS encapsulation provides protection, making the tape stable in repeated bending and pasting. This invention provides a new, efficient, convenient, reliable and easy-to-promote solution to the icing problem in cold environments.

[0080] It should be understood that any parts not described in detail in this specification belong to the prior art.

[0081] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for preparing a photothermal superhydrophobic anti-icing film layer on a copper tape substrate, characterized in that, include: (1) A honeycomb structure is formed on the copper foil surface of the conductive copper foil tape using laser etching technology, and then the tape is cleaned and dried to obtain the pretreated tape. (2) After mixing alkali, reducing agent, water and selenium powder, a reaction is carried out to obtain selenium ion precursor solution. The selenium ion precursor solution is mixed with water to obtain a selenium-containing solution. Water is added to the selenium-containing solution to dilute it and a reaction solution is obtained. The pretreated tape is immersed in the reaction solution for a constant temperature reaction. Then the tape after the constant temperature reaction is washed and dried to obtain a superhydrophilic H-Cu2Se substrate. (3) Mix polydimethylsiloxane, curing agent and dispersant to obtain a modified liquid, immerse the superhydrophilic H-Cu2Se substrate in the modified liquid to obtain an impregnated substrate, and cure the impregnated substrate to obtain a copper tape substrate photothermal superhydrophobic anti-icing film layer.

2. The preparation method according to claim 1, characterized in that, In step (1), the side length of the regular hexagonal unit in the honeycomb structure is 500-700μm, and the distance between two adjacent regular hexagonal units is 50-70μm.

3. The preparation method according to claim 1, characterized in that, In step (2), the alkali is selected from sodium hydroxide and / or potassium hydroxide; The reducing agent is selected from sodium borohydride and / or potassium borohydride; The weight ratio of the alkali, reducing agent and selenium powder is 50-100:1-3:

1.

4. The preparation method according to claim 1 or 2, characterized in that, In step (2), the alkali, reducing agent, water and selenium powder are mixed and reacted, wherein the weight ratio of water to alkali is 1.5-2:1; The reaction time is 2-10 minutes.

5. The preparation method according to claim 1, characterized in that, In step (2), the volume ratio of the selenium ion precursor solution to the selenium-containing solution is 1:3-5; The volume ratio of the selenium-containing solution to the reaction solution is 1:3-7.

6. The preparation method according to claim 1, characterized in that, In step (2), the conditions for the isothermal reaction include: a temperature of 10-30℃ and a time of 1-4 h.

7. The preparation method according to claim 1, characterized in that, In step (3), the dispersant is selected from one or more of n-hexane, cyclohexane and petroleum ether; The weight ratio of the polydimethylsiloxane to the curing agent is 8-12:1; The total content of polydimethylsiloxane and curing agent in the modified liquid is 1-15 wt%.

8. The preparation method according to claim 1, characterized in that, In step (3), the conditions for impregnation include: a temperature of 10-30℃ and a time of 5-1800s; The curing conditions include a temperature of 60-80℃ and a time of 2-8 hours.

9. A photothermal superhydrophobic anti-icing film layer on a copper tape substrate prepared by the preparation method according to any one of claims 1-8.

10. The application of the copper tape substrate photothermal superhydrophobic anti-icing and de-icing film layer according to claim 9 in low-temperature outdoor anti-icing and photothermal de-icing.

Images