Bionic flexible anti-icing and deicing composite material and preparation method thereof

Abstract

The invention discloses a bionic flexible anti-icing and deicing composite material and a preparation method thereof, and belongs to the technical field of composite material processing.The bionic flexible anti-icing and deicing composite material has the advantages that functional particles and phase change materials are introduced into a thermoplastic polymer matrix, and the functional particles remarkably improve the light absorptivity and conductivity of the material; according to the bionic flexible anti-icing and deicing composite material disclosed by the invention, the phase-change material blended inside efficiently absorbs and stores a large amount of latent heat, and when the environment temperature is reduced, the stored heat energy is released, so that not only is the deicing capability further enhanced, but also the anti-icing and deicing effects are improved. And the energy consumption is obviously reduced. Besides, a micro-nano composite structure constructed on the surface of the bionic flexible anti-icing and deicing composite material effectively reduces the actual contact area of a solid-liquid interface, a stable gas film layer is formed, and the material is endowed with excellent super-hydrophobic characteristic and self-cleaning capability, so that the passive anti-icing performance is remarkably improved.

Description

Technical Field

[0001] This invention relates to the field of composite material processing technology, specifically to a biomimetic flexible anti-icing and de-icing composite material and its preparation method. Background Technology

[0002] Icing poses a serious threat to critical sectors such as aviation, power, and transportation. Current mainstream de-icing technologies, such as electrothermal melting and mechanical removal, generally suffer from inherent limitations, including high energy consumption, potential damage to the substrate, or over-reliance on specific external conditions. While passive anti-icing materials can delay ice crystal formation to some extent, their ability to inhibit ice nucleation significantly decreases in extreme low-temperature environments, making them prone to failure. Although anti-icing and de-icing technologies are widely used and crucial in these fields, existing materials generally lack sufficient solar thermal conversion performance under extremely cold conditions. During the day, they cannot efficiently utilize the photothermal effect for active de-icing; at night, without sunlight, relying solely on passive anti-icing mechanisms is insufficient to effectively prevent icing. Therefore, improving the comprehensive anti-icing and de-icing performance of materials over a wide temperature range, especially under extremely cold conditions, is the core research direction for solving the problem of surface icing.

[0003] Based on this, existing research includes optimizing material production technology and formulation to improve the material's own de-icing ability. Patent application CN114644773A discloses a method for preparing an antifreeze, self-cleaning agricultural anti-fog greenhouse film, which mainly involves composited special inorganic nano-functional fillers into a polymer greenhouse film substrate such as PE or PVC. This functional filler primarily comprises nano-titanium dioxide surface-modified with a silane coupling agent. As a core photocatalyst, nano-titanium dioxide not only provides photo-induced superhydrophilicity and self-cleaning functions for decomposing organic matter, but also exhibits a photothermal effect during the day, especially under ultraviolet light, converting some light energy into heat energy, making the film surface temperature slightly higher than the ambient temperature, which helps prevent frost formation or promotes the melting of thin ice. However, because nano-titanium dioxide is prone to agglomeration, the photocatalytic activity and uniformity of the film material are poor, leading to the failure or localization of the self-cleaning and antifreeze functions. Summary of the Invention

[0004] This invention provides a biomimetic flexible anti-icing and de-icing composite material and its preparation method, which effectively solves the technical problem that existing anti-icing and de-icing materials generally have localized functions or even fail to achieve anti-icing and de-icing effects. This invention provides a biomimetic flexible anti-icing and de-icing composite material that achieves all-weather, efficient anti-icing and de-icing through the synergistic effect of active de-icing mechanism and passive anti-icing mechanism.

[0005] The first objective of this invention is to provide a biomimetic flexible anti-icing and de-icing composite material, wherein the biomimetic flexible anti-icing and de-icing composite material uses a thin film with a micron structure array as a matrix, and a coating formed by mixing hydrophobically modified first functional particles with polydimethylsiloxane is sprayed onto the matrix, and a micro-nano composite structure is formed on the surface of the matrix to obtain the biomimetic flexible anti-icing and de-icing composite material.

[0006] The film with the micron structure array is formed by melt blending a thermoplastic polymer as a matrix with second functional particles and a phase change material, followed by calendering.

[0007] The first functional particle and the second functional particle are each independently carbon nanotubes or graphene; the phase change material is PCM@PANI microcapsules.

[0008] In a preferred embodiment, the density of the micron structure array is 5 units / mm. 2 ~20 pieces / mm 2 The height is 10µm to 40µm, and the side length of the square base is 20µm; the size of the micro-nano composite structure is 0.1µm to 20µm.

[0009] In a preferred embodiment, the mass ratio of the thermoplastic polymer, the second functional particles, and the phase change material is 100:0.5 to 2.0:10.

[0010] In a preferred embodiment, the mass percentage of polydimethylsiloxane in the coating is 60% to 90%.

[0011] In a preferred embodiment, the hydrophobically modified second functional particle is specifically obtained by modifying the first functional particle at room temperature using octadecyltrichlorosilane as a modifier and n-hexane as a solvent to obtain the hydrophobically modified first functional particle. In the above modification process, the mass ratio of the first functional particle, octadecyltrichlorosilane, deionized water, and n-hexane is 4:2:1:40.

[0012] In a preferred embodiment, the mass ratio of the octadecyltrichlorosilane to the first functional particle is 1:2.

[0013] In a preferred embodiment, the thermoplastic polymer is one or more selected from polycaprolactone, polylactic acid, polyurethane, polystyrene, polyvinyl chloride, polyethylene, and phenolic resin.

[0014] A second objective of this invention is to provide a method for preparing the biomimetic flexible anti-icing and de-icing composite material described in any of the above claims, such as... Figure 1 As shown, it includes the following steps: A thermoplastic polymer is used as the matrix, and second functional particles and phase change materials are added and melt-blended to obtain a melt. The melt is then calendered to obtain a thin film with a micron-structure array.

[0015] Hydrophobically modified first functional particles are mixed with polydimethylsiloxane to obtain a coating. The coating is then sprayed onto the film with a micron structure array to form a micro-nano composite structure on the surface of the film, resulting in a biomimetic flexible anti-icing and de-icing composite material.

[0016] In a preferred embodiment, the calendering process specifically involves: melting and blending the thermoplastic polymer, the second functional particles, and the phase change material using a two-roll blending, internal mixing, open milling, or extrusion method to obtain a melt; casting the melt onto rollers and calendering it at a roller speed of 2 m / min to 4 m / min to obtain a film with a micron-structured array.

[0017] Compared with the prior art, the beneficial effects of the present invention are as follows: This invention provides a biomimetic flexible anti-icing and de-icing composite material. The material is prepared by spraying a coating formed from hydrophobically modified first functional particles and polydimethylsiloxane onto a film with a micron-structure array, forming a micro-nano composite structure on the film surface. The film with the micron-structure array is obtained by melt-blending a thermoplastic polymer with second functional particles and a phase change material, followed by calendering. This invention utilizes a thermoplastic polymer as a matrix, which is melt-blended with functional particles and phase change materials, followed by calendering to obtain a thin film with a micron-scale structure. In this film, the uniform distribution of functional particles and phase change materials within the matrix, along with the excellent interfacial bonding after calendering, creates a continuous and highly efficient thermal and electrical conductive network. This significantly improves the overall light absorption rate and electrical conductivity of the material, enabling rapid heating and heat absorption and storage under illumination or electrical conditions. This greatly enhances the active de-icing efficiency of the biomimetic flexible anti-icing and de-icing composite material. When the ambient temperature decreases, the stored heat energy is released, further strengthening the de-icing capability and significantly reducing energy consumption. Furthermore, the micro-nano composite structure constructed on the surface of the biomimetic flexible anti-icing and de-icing composite material effectively reduces the actual solid-liquid interface contact area, forming a stable gas film layer. This endows the material with excellent superhydrophobic properties and self-cleaning ability, thereby significantly improving passive anti-icing performance. This invention achieves all-weather, highly efficient anti-icing and de-icing effects of the biomimetic flexible anti-icing and de-icing composite material through the synergistic effect of the above-mentioned active de-icing mechanism and passive anti-icing mechanism.

[0018] The biomimetic flexible anti-icing and de-icing composite material provided by this invention solves the problem of ineffective anti-icing and de-icing under extremely cold conditions, improves the anti-icing and de-icing performance of polymer materials, and expands the application range of polymer cold-proof materials. The biomimetic flexible anti-icing and de-icing composite material provided by this invention exhibits good anti-icing and de-icing effects in agriculture, industry, transportation, and aerospace. Under solar radiation, the temperature of the composite material rapidly rises to 45°C, 18% higher than traditional anti-frost films. Under a 12V voltage, the composite material can quickly reach 40°C. At night, when no power is applied, the phase change material inside the composite material releases the absorbed latent heat, allowing the material to maintain a relatively high temperature. Therefore, under any conditions, the anti-icing effect maintains stable thermal regulation, effectively protecting crops from frost damage. The biomimetic flexible anti-icing and de-icing composite material prepared by this invention also avoids environmental problems through controlled degradation; after 150 days of exposure in soil, its mass loss rate is 9%. Attached Figure Description

[0019] Figure 1 This is a process flow diagram for preparing the biomimetic flexible anti-icing and de-icing composite material of the present invention, wherein 1 is a thermoplastic polymer, 2 is a first functional particle, 3 is a phase change material, 4 is a roller, 5 is a thin film with a micron structure array, 6 is a hydrophobic modifier, 7 is a solvent, 8 is a second functional particle, 9 is a hydrophobically modified second functional particle, 10 is polydimethylsiloxane, 11 is a coating, 12 is a spray gun, and 13 is the biomimetic flexible anti-icing and de-icing composite material.

[0020] Figure 2 SEM images of the thin film with a biomimetic micro-pyramid micron structure array prepared in Example 1 of this invention, wherein image a is 250 μm and image b is a magnified view of a portion of image a, 50 μm.

[0021] Figure 3 The images shown are SEM images of the micro-nano composite structure of Embodiment 4 of the present invention, where image a is 250 μm and image b is a magnified view of a portion of image a, at 50 μm.

[0022] Figure 4 The contact angle of the biomimetic flexible anti-icing and de-icing composite material of Example 4 of the present invention is the size of the surface of a 10µL water droplet under different pH conditions, silt conditions and salt solution conditions.

[0023] Figure 5 The images show photos of 10µL water droplets wetting the surface of the biomimetic flexible anti-icing and de-icing composite material of Example 4 of the present invention. In Figure a, the pH values ​​are 2, 4, 6, 8, and 10 from left to right under different pH conditions; Figure b shows the conditions under muddy water conditions; and Figure c shows the conditions under salt solution conditions, with the solutions from left to right being sodium carbonate solution, calcium chloride solution, ferric chloride solution, copper sulfate solution, and potassium ferricyanide solution.

[0024] Figure 6The diagram shows the process of ice melting into droplets and then rolling off under light and heat in the biomimetic flexible anti-icing and de-icing composite material of Embodiment 4 of the present invention. In the diagram, a shows ice beads adhering to the material surface before light exposure; b shows the droplets about to slide off after 30 seconds of light exposure; c shows the droplets sliding directly off the material surface after 30 seconds of light exposure and quickly sliding to the bottom of the material; and d shows the droplets completely rolling off with no droplet residue on the surface.

[0025] Figure 7 The diagram shows the process of ice melting into droplets and then rolling off under electric heating in the biomimetic flexible anti-icing and de-icing composite material of Embodiment 4 of the present invention. In the diagram, a shows ice beads adhering to the material surface before the current is applied; b shows the droplets about to slide off after 20 seconds of current application; c shows the droplets sliding off the material surface directly after 20 seconds of current application and quickly sliding to the bottom of the material; d shows the droplets completely rolling off with no droplet residue on the surface. Detailed Implementation

[0026] To enable those skilled in the art to better understand and implement the technical solutions of this invention, the invention is further described below with reference to specific embodiments. However, the embodiments are not intended to limit the invention. Unless otherwise specified, the following test methods and detection methods are conventional methods; unless otherwise specified, the reagents and raw materials are commercially available.

[0027] The background section of this invention mentions that patent application CN114644773A discloses a method for preparing an antifreeze, self-cleaning agricultural anti-fog greenhouse film. This method primarily involves composited special inorganic nano-functional fillers into a polymer greenhouse film substrate, such as PE or PVC. These functional fillers mainly comprise nano-titanium dioxide surface-modified with a silane coupling agent. As a core photocatalyst, nano-titanium dioxide not only provides photo-induced superhydrophilicity and self-cleaning functions for decomposing organic matter, but also exhibits a photothermal effect during the day (especially under ultraviolet light), converting some light energy into heat energy, making the film surface temperature slightly higher than the ambient temperature. This helps prevent frost formation or promotes the melting of thin ice. However, because nano-titanium dioxide is prone to agglomeration, the photocatalytic activity and uniformity of the film material are poor, leading to the failure or localization of the self-cleaning and antifreeze functions. To address these technical problems, this invention provides a biomimetic flexible anti-icing and de-icing composite material, its preparation method, and its application.

[0028] The technical solution of the present invention will be described in detail below.

[0029] This invention provides a biomimetic flexible anti-icing and de-icing composite material. The biomimetic flexible anti-icing and de-icing composite material uses a thin film with a micron-structure array as a matrix, and a coating formed by mixing hydrophobically modified first functional particles with polydimethylsiloxane is sprayed onto the matrix to form a micro-nano composite structure on the surface of the matrix, thus forming a biomimetic flexible anti-icing and de-icing composite material.

[0030] The film with the micron structure array is formed by melt blending a thermoplastic polymer as a matrix with second functional particles and a phase change material, followed by calendering.

[0031] The first functional particle and the second functional particle are each independently carbon nanotubes or graphene; the phase change material is PCM@PANI microcapsules.

[0032] In the above technical solution, a film with a micron-structured array is obtained by melt blending a thermoplastic polymer with functional particles and a phase change material, followed by calendering. In this film with a micron-structured array, the functional particles and phase change material are uniformly distributed in the matrix, and the calendering process creates a good interfacial bond, forming a continuous and highly efficient thermal and electrical conductive network within the film. This significantly improves the overall light absorption rate and electrical conductivity of the material, enabling rapid heating and heat absorption and storage under illumination or electrical conditions. This greatly enhances the active de-icing efficiency of the biomimetic flexible anti-icing and de-icing composite material of this invention. When the ambient temperature decreases, the stored heat energy is released, further strengthening the de-icing capability and significantly reducing energy consumption. Furthermore, the micro-nano composite structure constructed on the surface of the biomimetic flexible anti-icing and de-icing composite material effectively reduces the actual solid-liquid interface contact area, forming a stable gas film layer. This endows the material with excellent superhydrophobic properties and self-cleaning ability, thereby significantly improving passive anti-icing performance. This invention achieves all-weather, highly efficient anti-icing and de-icing effects of the biomimetic flexible anti-icing and de-icing composite material through the synergistic effect of the above-mentioned active de-icing mechanism and passive anti-icing mechanism.

[0033] The technical effects of the present invention will be described below through specific embodiments and comparative examples.

[0034] The PCM@PANI microcapsules used in the subsequent embodiments of the present invention were purchased from Hebei Ruosen Technology Co., Ltd., and their shell material is polymethyl methacrylate, their core material is n-octadecane, and their phase transition temperature is 40°.

[0035] Example 1 A method for preparing a biomimetic flexible anti-icing and de-icing composite material includes the following steps: S1, 500g of polycaprolactone, 2.5g of carbon nanotube particles with a particle size of 0.5µm to 1µm, and 50g of PCM@PANI microcapsules were blended using a biaxial eccentric rotor extruder. The mixture was then melt-plasticized in stages using the extruder, and the melt was cast onto a custom roller. At a roller speed of 3m / min, the melt was calendered using micro-roll forming technology to form a film with a biomimetic micropyramid microstructure array. The density of the biomimetic micropyramid microstructure array was 10 particles / mm². 2 The height is 15µm, the square base side length is 20µm, and the spacing is 10µm.

[0036] S2, 2g of octadecyltrichlorosilane and 1g of deionized water were added to 4g of graphene, followed by the addition of 40g of n-hexane as a solvent. The mixture was stirred at room temperature for 3 hours and then dried at 40°C to obtain modified graphene. The modified graphene was mixed with polydimethylsiloxane to obtain a coating, wherein the polydimethylsiloxane content in the coating was 70% by mass. The coating was sprayed using a vapor deposition method at 60°C for 30 minutes to form a low surface energy coating with a square topological structure and a side length of 20µm micro-nano composite structure, resulting in a biomimetic flexible anti-icing and de-icing composite material.

[0037] Example 2 A method for preparing a biomimetic flexible anti-icing and de-icing composite material includes the following steps: S1, 500g of polycaprolactone, 7.5g of carbon nanotube particles with a particle size of 0.5µm to 1µm, and 50g of PCM@PANI microcapsules were blended using a biaxial eccentric rotor extruder. The mixture was then melt-plasticized in stages using the extruder, and the melt was cast onto a custom roller. At a roller speed of 2m / min, the melt was calendered using micro-roll forming technology to form a film with a biomimetic micropyramid microstructure array. The density of the biomimetic micropyramid microstructure array was 10 particles / mm². 2 The height is 15µm, the square base side length is 20µm, and the spacing is 10µm.

[0038] S2, 2g of octadecyltrichlorosilane and 1g of deionized water were added to 4g of graphene, followed by the addition of 40g of n-hexane as a solvent. The mixture was stirred at room temperature for 3 hours and then dried at 40°C to obtain modified graphene. The modified graphene was mixed with polydimethylsiloxane to obtain a coating, wherein the polydimethylsiloxane content in the coating was 60% by mass. The coating was sprayed using a vapor deposition method at 60°C for 30 minutes to form a low surface energy coating with a square topological structure and a side length of 20µm micro-nano composite structure, resulting in a biomimetic flexible anti-icing and de-icing composite material.

[0039] Example 3 A method for preparing a biomimetic flexible anti-icing and de-icing composite material includes the following steps: 500g of polycaprolactone, 10g of carbon nanotube particles with a particle size of 0.5µm to 1µm, and 50g of PCM@PANI microcapsules were blended using a biaxial eccentric rotor extruder. The mixture was then melt-plasticized in stages using the extruder, and the melt was cast onto a custom roller. At a roller speed of 4m / min, the melt was calendered using micro-roll forming technology to form a film with a biomimetic micropyramid microstructure array. The density of the biomimetic micropyramid microstructure array was 10 particles / mm². 2 The height is 15µm, the square base side length is 20µm, and the spacing is 10µm.

[0040] S2, 2g of octadecyltrichlorosilane and 1g of deionized water were added to 4g of graphene, followed by the addition of 40g of n-hexane as a solvent. The mixture was stirred at room temperature for 3 hours and then dried at 40°C to obtain modified graphene. The modified graphene was mixed with polydimethylsiloxane to obtain a coating, wherein the polydimethylsiloxane content in the coating was 90% by mass. The coating was sprayed using a vapor deposition method at 60°C for 30 minutes to form a low surface energy coating with a square topological structure and a side length of 20µm micro-nano composite structure, resulting in a biomimetic flexible anti-icing and de-icing composite material.

[0041] To further illustrate the technical effects of the present invention, a comparative example is provided, as follows.

[0042] Comparative Example 1 The difference compared to Example 1 is that phase change materials and modified graphene are not used.

[0043] A method for preparing an anti-icing material includes the following steps: S1. After blending 500g of polycaprolactone with 2.5g of carbon nanotubes, the melt was injected into a mold cavity under template-free conditions to obtain a square polymer sheet.

[0044] S2, Polydimethylsiloxane (PDMS) and curing agent dibutyltin dilaurate (DBTL) are mixed at a mass ratio of 10:1 and sprayed onto the surface of the square polymer sheet to obtain an anti-icing material.

[0045] Comparative Example 2 The difference compared to Example 2 is that phase change materials are not used.

[0046] A method for preparing a biomimetic flexible anti-icing and de-icing composite material includes the following steps: S1, 500g of polycaprolactone and 7.5g of carbon nanotubes with a particle size of 0.5µm to 1µm were subjected to a two-stage melt blending process. The mixture was then melt-plasticized in stages using an extruder. The melt was cast onto a custom roller and calendered using micro-roll forming technology to form a film with a square topological microstructure array. The density of the square topological microstructure array was 10 nanotubes / mm². 2 The height is 15µm, the square base side length is 20µm, and the spacing is 10µm.

[0047] S2, 2g of octadecyltrichlorosilane and 1g of deionized water were added to 4g of graphene, followed by the addition of 40g of n-hexane as a solvent. The mixture was stirred at room temperature for 3 hours and then dried at 40°C to obtain modified graphene. The modified graphene was mixed with polydimethylsiloxane to obtain a coating, wherein the polydimethylsiloxane content in the coating was 60% by mass. The coating was uniformly sprayed onto the surface of a film with a square topological micron structure array using a spray gun, forming a micro-nano composite structure with a square topological structure side length of 20µm on the film surface, thus obtaining a biomimetic flexible anti-icing and de-icing composite material.

[0048] Comparative Example 3 The difference from Example 1 is that phase change materials are not used.

[0049] A method for preparing a biomimetic flexible anti-icing and de-icing composite material includes the following steps: S1, 500g of polycaprolactone and 2.5g of carbon nanotubes with a particle size of 0.5µm to 1µm are subjected to a two-stage melt blending process. The mixture is then melt-plasticized in stages using an extruder. The melt is cast onto a custom roller and calendered using micro-roll forming technology to form a film with a square topological microstructure array. The density of the square topological microstructure array is 10 nanotubes / mm². 2 The height is 15µm, the square base side length is 20µm, and the spacing is 10µm.

[0050] S2, 2g of octadecyltrichlorosilane and 1g of deionized water were added to 4g of graphene, followed by the addition of 40g of n-hexane as a solvent. The mixture was stirred at room temperature for 3 hours and then dried at 40°C to obtain modified graphene. The modified graphene was mixed with polydimethylsiloxane to obtain a coating, wherein the polydimethylsiloxane content in the coating was 70% by mass. The coating was uniformly sprayed onto the surface of a film with a square topological micron structure array using a spray gun, forming a micro-nano composite structure with a square topological structure side length of 20µm on the film surface, thus obtaining a biomimetic flexible anti-icing and de-icing composite material.

[0051] Comparative Example 4 The difference from Example 3 is that phase change materials are not used.

[0052] A method for preparing a biomimetic flexible anti-icing and de-icing composite material includes the following steps: 500g of polycaprolactone and 10g of carbon nanotubes with a particle size of 0.5µm to 1µm were subjected to a two-stage melt blending process. The mixture was then melt-plasticized in stages using an extruder. The melt was cast onto a custom roller and calendered using micro-roll forming technology to form a film with a square topological microstructure array. The density of the square topological microstructure array was 10 nanotubes / mm². 2The height is 15µm, the square base side length is 20µm, and the spacing is 10µm.

[0053] S2, 2g of octadecyltrichlorosilane and 1g of deionized water were added to 4g of graphene, followed by the addition of 40g of n-hexane as a solvent. The mixture was stirred at room temperature for 3 hours and then dried at 40°C to obtain modified graphene. The modified graphene was mixed with polydimethylsiloxane to obtain a coating, wherein the polydimethylsiloxane content in the coating was 70% by mass. The coating was uniformly sprayed onto the surface of a film with a square topological micron structure array using a spray gun, forming a micro-nano composite structure with a square topological structure side length of 20µm on the film surface, thus obtaining a biomimetic flexible anti-icing and de-icing composite material.

[0054] The performance of the biomimetic flexible anti-icing and de-icing composite materials prepared in the embodiments of the present invention and the anti-icing materials prepared in Comparative Examples 1 to 4 were characterized, and the results are as follows.

[0055] Figure 2 SEM images of the thin film with a biomimetic micropyramid array of micrometer structures prepared in Example 1 of this invention are shown, where image a is 250 μm and image b is a magnified view of image a, at 50 μm. Figure 2 It can be seen that the surface of the film with the biomimetic micro pyramid microstructure array in Example 1 was micro-rolled to form a neat square topology.

[0056] Figure 3 These are SEM images of the micro-nano composite structure of Embodiment 1 of the present invention, where image a is 250 μm and image b is a magnified view of a portion of image a, at 50 μm. Figure 3 It can be seen that a low surface energy coating with micro-nano structure has been successfully formed on the surface of the thin film.

[0057] Figure 4 Photographs showing the wetting state of a 10µL water droplet on the surface of the biomimetic flexible all-weather anti-icing and de-icing composite material of Example 1 under different conditions. Figure 4 It can be seen that the contact angle of a 10µL water droplet remains above 158° under different pH conditions, silt conditions, and salt solution conditions, demonstrating excellent superhydrophobic properties.

[0058] Figure 5 The images show photographs of 10µL water droplets wetting the surface of the biomimetic flexible anti-icing and de-icing composite material of Example 1 of this invention. Image a shows different pH conditions, from left to right: pH 2, 4, 6, 8, 10; image b shows mud conditions, with mud concentrations from left to right: 20%, 30%, 40%, 50%, 60%; image c shows salt solution conditions, from left to right: sodium carbonate solution, calcium chloride solution, ferric chloride solution, copper sulfate solution, and potassium ferricyanide solution. Figure 5It can be seen that the square topology and micro-nano structure on the surface of the composite material enhance the wettability of the composite material, providing more attachment sites for tiny water droplets, causing the superhydrophobic surface of the material to exhibit point-like hydrophilic properties, thus making the material as a whole exhibit a hydrophobic "air cushion". When water droplets fall on the surface of the material, they form a solid-liquid-gas three-phase composite interface, reducing solid-liquid contact and preventing water droplets from further wetting the material, so that the anti-icing material exhibits a large contact angle.

[0059] Figure 6 and Figure 7 The images depict the process of ice melting into droplets and then rolling off under photothermal and electrothermal conditions, respectively, in the biomimetic flexible all-weather anti-icing and de-icing composite material. When exposed to sunlight, the filled carbon nanotubes and the surface micro-nano surface synergistically absorb sunlight, causing a rapid temperature increase and melting the ice droplets. When electricity is applied, the internally filled carbon nanotubes form a complete conductive network, raising the temperature through electrothermal heating and melting the ice droplets. The material exhibits excellent de-icing capabilities. The measured performance of the anti-icing material is shown in Table 1.

[0060] Table 1. Performance Comparison of Composite Materials in Embodiments and Comparative Examples of the Invention As can be seen from the data in the table, the biomimetic flexible anti-icing and de-icing composite material prepared in this application has improved its comprehensive mechanical properties and photothermal and electrothermal properties by filling with functional particles and phase change materials and improving the molding process, resulting in an anti-icing material with excellent performance.

[0061] Obviously, those skilled in the art can make various modifications and variations to this invention without departing from its spirit and scope. Therefore, if these modifications and variations fall within the scope of the claims of this invention and their equivalents, this invention also intends to include these modifications and variations.

Claims

1. A biomimetic flexible anti-icing and de-icing composite material, characterized in that, The biomimetic flexible anti-icing and de-icing composite material uses a thin film with a micron structure array as the matrix, and a coating formed by mixing hydrophobically modified first functional particles with polydimethylsiloxane is sprayed onto the matrix to form a micro-nano composite structure on the surface of the matrix, thus obtaining the biomimetic flexible anti-icing and de-icing composite material. The film with the micron structure array is formed by melt blending a thermoplastic polymer as a matrix with second functional particles and a phase change material, followed by calendering. The first functional particle and the second functional particle are each independently carbon nanotubes or graphene; the phase change material is PCM@PANI microcapsules.

2. The biomimetic flexible anti-icing and de-icing composite material according to claim 1, characterized in that, The density of the microstructure array is 5 units / mm. 2 ~20 pieces / mm 2 The height is 10µm to 40µm, and the side length of the square base is 20µm; the size of the micro-nano composite structure is 0.1µm to 20µm.

3. The biomimetic flexible anti-icing and de-icing composite material according to claim 1, characterized in that, The mass ratio of the thermoplastic polymer, the second functional particles, and the phase change material is 100:0.5 to 2.0:

10.

4. The biomimetic flexible anti-icing and de-icing composite material according to claim 1, characterized in that, The coating contains 60% to 90% polydimethylsiloxane by mass.

5. The biomimetic flexible anti-icing and de-icing composite material according to claim 1, characterized in that, The hydrophobically modified second functional particle is specifically obtained by modifying the first functional particle at room temperature using octadecyltrichlorosilane as a modifier and n-hexane as a solvent to obtain the hydrophobically modified first functional particle.

6. The biomimetic flexible anti-icing and de-icing composite material according to claim 5, characterized in that, The mass ratio of the octadecyltrichlorosilane to the first functional particle is 1:

2.

7. The biomimetic flexible anti-icing and de-icing composite material according to claim 1, characterized in that, The thermoplastic polymer is one or more of polycaprolactone, polylactic acid, polyurethane, polystyrene, polyvinyl chloride, polyethylene, and phenolic resin.

8. A method for preparing the biomimetic flexible anti-icing and de-icing composite material according to any one of claims 1 to 7, characterized in that, Includes the following steps: A thermoplastic polymer is used as a matrix, and second functional particles and phase change materials are added and melt-blended to obtain a melt. The melt is then calendered to obtain a thin film with a micron-structured array. Hydrophobically modified first functional particles are mixed with polydimethylsiloxane to obtain a coating. The coating is then sprayed onto the film with a micron structure array to form a micro-nano composite structure on the surface of the film, resulting in a biomimetic flexible anti-icing and de-icing composite material.

9. The preparation method of the biomimetic flexible anti-icing and de-icing composite material according to claim 8, characterized in that, The calendering process specifically involves: melting and blending thermoplastic polymer, second functional particles, and phase change material using a two-roll blending, internal mixing, open milling, or extrusion method to obtain a melt; casting the melt onto rollers and calendering it at a roller speed of 2 m / min to 4 m / min to obtain a film with a micron-structured array.

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