Super-hydrophobic graphene electric heating film and preparation method thereof

Abstract

The application relates to the technical field of laser processing, in particular to a super-hydrophobic graphene electric heating film and a preparation method thereof. The graphene electric heating film comprises an organic material base, one side of the organic material base is distributed with a wavy micro-groove array structure, and the other side is covered with a conductive graphene layer; the preparation method comprises the following steps: irradiating the surface of the organic material base with a laser with a power of 5W-20W to etch a micro-groove array structure; irradiating the surface of the micro-groove array structure with a laser with a power of 1W-4W to form super-hydrophobicity of the micro-groove array structure; and irradiating the other side of the organic material base with a laser to induce a conductive graphene layer. Through the super-hydrophobic graphene electric heating film and the preparation method thereof, the problem of poor anti-icing and de-icing effect can be effectively solved, the preparation method is simple and controllable, and the super-hydrophobic graphene electric heating film has large-area application capability.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of laser processing, in particular to a super-hydrophobic graphene electric heating film and a preparation method thereof. BACKGROUND

[0002] When an airplane flies in an environment below the freezing point, icing phenomenon will occur. Icing on some parts of the surface of the airplane will reduce the lift coefficient of the airplane and increase the drag coefficient, affecting the maneuverability and stability of the airplane, and even causing the airplane to lose control and crash. Therefore, the anti-icing and de-icing technology of the airplane has always been an important research topic in airplane design. At present, the electric heating anti-icing and de-icing method is widely used on large airplanes, but unmanned aerial vehicles with insufficient on-board electric power cannot use this method.

[0003] Current research shows that super-hydrophobic surfaces have anti-icing properties, not only delaying the icing time, but also reducing the adhesion of ice. In the prior art, a Chinese invention patent document with publication number CN114211121A and publication date March 22, 2022 is proposed. The technical solution disclosed in the patent document is as follows: a femtosecond laser ablation-surface coating composite processing method of a super-hydrophobic surface, first etching the surface of a substrate material sample using a femtosecond pulse laser to obtain a material sample with a micro-nano array surface; then coating a low-energy state hydrophobic film on the material sample with a micro-nano array surface to obtain a low-energy state hydrophobic film-micro-nano array structure surface composite material, achieving comprehensive hydrophobic performance of physical hydrophobicity and chemical hydrophobicity.

[0004] The above technical solution has the following problems in actual use: the technical solution is mainly aimed at intrinsic hydrophilic materials, that is, laser ablation plus additional introduction of low surface energy substances, but the preparation method is complex and uncontrollable, and is not suitable for large-area production.

[0005] Further, in certain environments, ice formation still occurs on super-hydrophobic surfaces, and the anti-icing effect cannot be achieved. Both electric heating methods and super-hydrophobic methods can achieve certain anti-icing and de-icing effects, but both have specific shortcomings. If the two methods are integrated together, the advantages are complementary, and better anti-icing and de-icing effects can be achieved. In the prior art, a Chinese patent application with the publication number CN110423523A and the publication date of November 8, 2019 is disclosed, and the technical solution disclosed in the patent document is as follows: A super-hydrophobic de-icing composite coating and a preparation method thereof, the preparation method comprising: after surface cleaning treatment of a base material, spraying an insulating organic coating on the surface of the base to form an insulating layer; arranging electrodes uniformly distributed on the surface of the insulating layer, the electrode distribution being arranged according to the coverage range of the heating layer, and the heating layer range being uniformly divided; uniformly applying a heating coating containing graphene filler to the surface of the electrode and the insulating layer to form a heating coating, wherein the heating filler can be graphene or a mixed filler of graphene and Ag metal; mixing a low-surface-energy solvent and nano-sized SiO2 by a dispersion process to obtain a hydrophobic coating, and then coating the hydrophobic coating on the surface of the heating coating to form a hydrophobic coating; and uniformly processing a concave-convex micro-nano structure on the surface of the hydrophobic coating by laser or micro-embossing to improve the hydrophobicity of the coating.

[0006] The above technical solution has the following problems in actual use: the preparation process involves the insulating layer, the electrode, the heating coating, the hydrophobic coating, and the processing of the micro-nano structure, and the process is relatively complex, which is not conducive to large-area use; the thickness of the entire composite coating system reaches 200μm or more, and the weight increases too much, which is not suitable for the unmanned aerial vehicle anti-icing and de-icing field which has strict requirements on weight. SUMMARY

[0007] To solve the above technical problems, the present application provides a super-hydrophobic graphene electric heating film and a preparation method thereof, which can effectively solve the problem of poor anti-icing and de-icing effect, and the preparation method is simple and controllable, and has large-area application capability.

[0008] The present application is realized by adopting the following technical solutions:

[0009] A super-hydrophobic graphene electric heating film, characterized in that: comprising an organic material base, one side of the organic material base is distributed with a wave-shaped micro-scale groove array structure with super-hydrophobic properties etched by laser, and the other side is covered with a conductive graphene layer.

[0010] The material of the organic material base is polyimide, polyether ether ketone, polysulfone, phenolic resin, or polyphenylene sulfide.

[0011] The period of the micro-scale groove array structure is 20μm~100μm, and the height is 20μm~50μm, wherein the period refers to the distance between the bottoms of adjacent grooves.

[0012] The thickness of the conductive graphene layer is 20-50 mu m, and the square resistance is 35-1000 ohm / sq.

[0013] A preparation method of super-hydrophobic graphene electric heating film, characterized in that it comprises the following steps:

[0014] S1. irradiating the surface of the organic material substrate with a laser with a power of 5-20 W to etch a micron-level groove array structure;

[0015] S2. irradiating the surface of the micron-level groove array structure with a laser with a power of 1-4 W to form super-hydrophobicity of the micron-level groove array structure;

[0016] S3. irradiating the other side of the organic material substrate with a laser to induce a conductive graphene layer.

[0017] The type of the laser in the steps S1, S2 and S3 is a carbon dioxide laser, and the moving mode of the laser beam is parallel line scanning, and the scanning line spacing is 20-100 mu m.

[0018] The power of the laser in the step S3 is 5-20 W.

[0019] Compared with the prior art, the present application has the following advantages:

[0020] 1. In the present application, the super-hydrophobic function and the heating function are realized by different structures, the micron-level groove array structure realizes the super-hydrophobic function, and the conductive graphene layer realizes the heating function. Moreover, the different structures are distributed on both sides of the film, ingeniously integrating the two functions, and the space is separated, and the process control is simple. Both super-hydrophobicity and heating can achieve anti-icing effect, the integration of the two functions can realize complementary advantages, and better anti-icing effect can be obtained, and the introduction of super-hydrophobicity can reduce the energy consumption of heating, achieving the purpose of high efficiency and energy saving.

[0021] 2. In the present application, the super-hydrophobic function and the heating function are realized by laser as a tool, and the micron-level structure and the low surface energy substance are generated on the surface of the organic material substrate by twice laser treatment with different powers, and the conductive graphene layer is induced and formed by laser treatment, the whole preparation process is simple and controllable, and the automatic capacity of laser treatment can realize large-area production and application.

[0022] 3、In the application, first, the laser with power of 5W~20W is used to process, which can form the wave-shaped micron-sized groove array structure on the surface of the organic material substrate, and the surface material is changed into graphene. The graphene itself has certain hydrophobicity, but the graphene surface generated by the high-power laser processing is covered with a large number of oxygen-containing groups, so that it presents hydrophilicity. Then, the laser with power of 1W~4W is used to process, which can remove the oxygen-containing groups on the graphene surface, expose more hydrophobic carbon-containing groups, and the micron-sized groove array structure still exists, so that the super-hydrophobicity is finally presented. In summary, the preparation method in the application can generate the surface micro-nano structure and low surface energy substance at the same time. BRIEF DESCRIPTION OF DRAWINGS

[0023] The application will be further described in detail below with reference to the accompanying drawings and specific embodiments, in which:

[0024] Figure 1 It is a structural schematic diagram of the application;

[0025] Figure 2 It is a flowchart of the preparation method in the application;

[0026] Markings in the figure:

[0027] 1, organic material substrate, 2, micron-sized groove array structure, 3, conductive graphene layer. DETAILED DESCRIPTION

[0028] Example 1

[0029] This embodiment includes a super-hydrophobic graphene electric heating film, which includes an organic material substrate 1. The material of the organic material substrate 1 can be polyimide in particular. One side of the organic material substrate 1 is distributed with the wave-shaped micron-sized groove array structure 2 with super-hydrophobicity which is etched out by laser, and the other side is covered with a conductive graphene layer 3.

[0030] More specifically, the preparation method of the above-mentioned super-hydrophobic graphene electric heating film can be as follows:

[0031] S1. The surface of the 125μm thick polyimide film is wiped clean with anhydrous ethanol, and the film surface is irradiated with a high-power carbon dioxide laser to etch out the micron-sized groove array structure 2. The laser power is 5W, and the scanning line spacing is 20μm. The period of the micron-sized groove array structure 2 is 20μm, and the height is 20μm. Among them, the period refers to the distance between the bottoms of adjacent grooves.

[0032] S2. A lower-power carbon dioxide laser is used to irradiate the surface of the above-mentioned micron-sized groove array structure 2, wherein the laser power is 1W, and the scanning line spacing is 20μm.

[0033] S3. The other side of the polyimide film is irradiated by a carbon dioxide laser, wherein the laser power is 5 W and the scanning line spacing is 20 μm, to obtain the super-hydrophobic graphene electric heating film.

[0034] After testing, the thickness of the conductive graphene layer 3 is 20 μm, and the sheet resistance is 35 Ω / sq. The water droplet contact angle of the finally obtained polyimide-based graphene electric heating film is 150.5°, indicating that it has super-hydrophobic properties.

[0035] Embodiment 2

[0036] This embodiment includes a super-hydrophobic graphene electric heating film, which comprises an organic material matrix 1. The material of the organic material matrix 1 can be polyimide. The one side of the organic material matrix 1 is distributed with a wavy micron-sized groove array structure 2 etched by a laser, and the other side is covered with a conductive graphene layer 3.

[0037] More specifically, the preparation method of the super-hydrophobic graphene electric heating film can be as follows:

[0038] S1. The surface of a 200 μm thick polyimide film is wiped clean with anhydrous ethanol, and the surface of the film is irradiated by a carbon dioxide laser with high power to etch a micron-sized groove array structure 2. The laser power is 20 W, and the scanning line spacing is 100 μm. The period of the micron-sized groove array structure 2 is 100 μm, and the height is 50 μm. The period refers to the distance between the bottoms of adjacent grooves.

[0039] S2. The surface of the above micron-sized groove array structure 2 is irradiated by a carbon dioxide laser with low power, wherein the laser power is 4 W and the scanning line spacing is 100 μm.

[0040] S3. The other side of the polyimide film is irradiated by a carbon dioxide laser, wherein the laser power is 20 W and the scanning line spacing is 100 μm, to obtain the super-hydrophobic graphene electric heating film.

[0041] After testing, the thickness of the conductive graphene layer 3 is 50 μm, and the sheet resistance is 1000 Ω / sq. The water droplet contact angle of the finally obtained polyimide-based graphene electric heating film is 152.3°, indicating that it has super-hydrophobic properties.

[0042] Embodiment 3

[0043] This embodiment includes a super-hydrophobic graphene electric heating film, which comprises an organic material matrix 1. The material of the organic material matrix 1 can be polyimide. The one side of the organic material matrix 1 is distributed with a wavy micron-sized groove array structure 2 etched by a laser, and the other side is covered with a conductive graphene layer 3. Figure 1, including an organic material substrate 1. The material of the organic material substrate 1 can be polyimide. One side of the organic material substrate 1 is distributed with a wavy micron-sized groove array structure 2 with super-hydrophobic properties etched by laser, and the other side is covered with a conductive graphene layer 3.

[0044] More specifically, referring to the drawings attached to the specification Figure 2 The preparation method of the super-hydrophobic graphene electric heating film can be as follows:

[0045] S1. The surface of a 125-micron-thick polyimide film is wiped clean with anhydrous ethanol, and a high-power carbon dioxide laser is used to irradiate the surface of the film to etch a micron-sized groove array structure 2. The laser power is 5.25 W, and the scanning line spacing is 20 microns. The period of the micron-sized groove array structure 2 is 20 microns, and the height is 25 microns. The period refers to the distance between the bottoms of adjacent grooves.

[0046] S2. A lower-power carbon dioxide laser is used to irradiate the surface of the micron-sized groove array structure 2, with a laser power of 2.25 W and a scanning line spacing of 20 microns.

[0047] S3. A carbon dioxide laser is used to irradiate the other side of the polyimide film, with a laser power of 5.25 W and a scanning line spacing of 80 microns, to obtain a super-hydrophobic graphene electric heating film.

[0048] After testing, the thickness of the graphene layer is 25 microns, and the sheet resistance is 120 Ω / sq. The water droplet contact angle of the final polyimide-based graphene electric heating film is 150.5°, indicating that it has super-hydrophobic properties.

[0049] Example 4

[0050] This embodiment includes a super-hydrophobic graphene electric heating film, including an organic material substrate 1. The material of the organic material substrate 1 can be polyimide. One side of the organic material substrate 1 is distributed with a wavy micron-sized groove array structure 2 with super-hydrophobic properties etched by laser, and the other side is covered with a conductive graphene layer 3.

[0051] More specifically, the preparation method of the super-hydrophobic graphene electric heating film can be as follows:

[0052] S1. The surface of a 125-micron-thick polyimide film is wiped clean with anhydrous ethanol, and a high-power carbon dioxide laser is used to irradiate the surface of the film to etch a micron-sized groove array structure 2. The laser power is 5.25 W, and the scanning line spacing is 20 microns. The period of the micron-sized groove array structure 2 is 20 microns, and the height is 25 microns. The period refers to the distance between the bottoms of adjacent grooves.

[0053] S2. Adopting a lower power carbon dioxide laser to irradiate the surface of the above-mentioned micron-sized groove array structure 2, wherein the laser power is 3W, and the scanning line spacing is 40μm.

[0054] S3. Adopting a carbon dioxide laser to irradiate the other side of the polyether ether ketone film, wherein the laser power is 10W, and the scanning line spacing is 100μm, to finally obtain the super-hydrophobic graphene electric heating film.

[0055] After testing, the thickness of the conductive graphene layer 3 is 30μm, and the square resistance is 192Ω / sq. The water droplet contact angle of the finally obtained polyether ether ketone-based graphene electric heating film is 151.2°, indicating that it has super-hydrophobic properties.

[0056] Example 5

[0057] This embodiment includes a super-hydrophobic graphene electric heating film, which comprises an organic material matrix 1. The material of the organic material matrix 1 can be specifically polyether ether ketone. The one side of the organic material matrix 1 is distributed with a wavy micron-sized groove array structure 2 etched by laser, and the other side is covered with a conductive graphene layer 3.

[0058] More specifically, the preparation method of the above-mentioned super-hydrophobic graphene electric heating film can be specifically as follows:

[0059] S1. The surface of a 500μm thick polyether ether ketone film is wiped clean with anhydrous ethanol, and a higher power carbon dioxide laser is used to irradiate the surface of the film to etch a micron-sized groove array structure 2. The laser power is 10W, and the scanning line spacing is 40μm. The period of the micron-sized groove array structure 2 is 40μm, and the height is 30μm. Among them, the period refers to the distance between the bottoms of adjacent grooves.

[0060] S2. Adopting a lower power carbon dioxide laser to irradiate the surface of the above-mentioned micron-sized groove array structure 2, wherein the laser power is 3W, and the scanning line spacing is 40μm.

[0061] S3. Adopting a carbon dioxide laser to irradiate the other side of the polyether ether ketone film, wherein the laser power is 10W, and the scanning line spacing is 100μm, to finally obtain the super-hydrophobic graphene electric heating film.

[0062] After testing, the thickness of the conductive graphene layer 3 is 30μm, and the square resistance is 192Ω / sq. The water droplet contact angle of the finally obtained polyether ether ketone-based graphene electric heating film is 151.2°, indicating that it has super-hydrophobic properties.

[0063] Example 6

[0064] The embodiment includes a super-hydrophobic graphene electric heating film, which comprises an organic material substrate 1. The material of the organic material substrate 1 can be phenolic resin. The organic material substrate 1 is provided with a micrometer-scale groove array structure 2 with super-hydrophobic properties in a wave shape on one side, and is covered with a conductive graphene layer 3 on the other side.

[0065] More specifically, the preparation method of the super-hydrophobic graphene electric heating film can be as follows:

[0066] S1. The surface of a 500-μm-thick phenolic resin film is wiped clean with anhydrous ethanol, and a high-power carbon dioxide laser is used to irradiate the surface of the film to etch a micrometer-scale groove array structure 2. The laser power is 10 W, and the scanning line spacing is 40 μm. The period of the micrometer-scale groove array structure 2 is 40 μm, and the height is 30 μm. The period refers to the distance between the bottoms of adjacent grooves.

[0067] S2. A low-power carbon dioxide laser is used to irradiate the surface of the micrometer-scale groove array structure 2, wherein the laser power is 3 W, and the scanning line spacing is 40 μm.

[0068] S3. A carbon dioxide laser is used to irradiate the other side of the phenolic resin film, wherein the laser power is 10 W, and the scanning line spacing is 100 μm, to obtain a super-hydrophobic graphene electric heating film.

[0069] After testing, the thickness of the conductive graphene layer 3 is 30 μm, and the square resistance is 184 Ω / sq. The water droplet contact angle of the final phenolic resin-based graphene electric heating film is 151.5°, indicating that it has super-hydrophobic properties.

[0070] Embodiment 7

[0071] The embodiment includes a super-hydrophobic graphene electric heating film, which comprises an organic material substrate 1. The material of the organic material substrate 1 can be polyphenylene sulfide. The organic material substrate 1 is provided with a micrometer-scale groove array structure 2 with super-hydrophobic properties in a wave shape on one side, and is covered with a conductive graphene layer 3 on the other side.

[0072] More specifically, the preparation method of the super-hydrophobic graphene electric heating film can be as follows:

[0073] S1. The surface of a 100-μm-thick polyphenylene sulfide film is wiped clean with anhydrous ethanol, and a high-power carbon dioxide laser is used to irradiate the surface of the film to etch a micrometer-scale groove array structure 2. The laser power is 7.5 W, and the scanning line spacing is 40 μm. The period of the micrometer-scale groove array structure 2 is 40 μm, and the height is 30 μm. The period refers to the distance between the bottoms of adjacent grooves.

[0074] S2. The surface of the above-mentioned micron-sized groove array structure 2 is irradiated by a low-power carbon dioxide laser, wherein the laser power is 3W and the scanning line spacing is 40μm.

[0075] S3. The other side of the polyphenylene sulfide film is irradiated by a carbon dioxide laser, wherein the laser power is 10W and the scanning line spacing is 100μm, and finally an ultra-hydrophobic graphene electric heating film is obtained.

[0076] After testing, the thickness of the conductive graphene layer 3 is 30μm, and the square resistance is 180Ω / sq. The water droplet contact angle of the finally obtained polyphenylene sulfide-based graphene electric heating film is 151.3°, indicating that it has ultra-hydrophobic properties.

[0077] In summary, after reading the present application document, the person skilled in the art can make various corresponding transformation schemes according to the technical solutions and technical concepts of the present application without creative mental labor, which all belong to the scope protected by the present application.

Claims

1. A method for preparing a superhydrophobic graphene electric heating film, characterized in that: The method comprises the following steps: S1. irradiating the surface of an organic material substrate (1) with a laser having a power of 5 W to 20 W to etch a micron-scale groove array structure (2); the material of the organic material substrate (1) is polyimide, polyether ether ketone, polysulfone, phenolic resin or polyphenylene sulfide; S2. irradiating the surface of the micron-scale groove array structure (2) with a laser having a power of 1 W to 4 W to form superhydrophobicity of the micron-scale groove array structure (2); S3. irradiating the other side of the organic material substrate (1) with a laser to induce a conductive graphene layer (3).

2. The method for preparing a superhydrophobic graphene electrothermal film according to claim 1, characterized in that: The laser in steps S1, S2 and S3 is a carbon dioxide laser, and the laser beam moves in parallel line scanning, and the scanning line spacing is 20 μm to 100 μm.

3. The method for preparing a superhydrophobic graphene electrothermal film according to claim 2, characterized in that: The power of the laser in step S3 is 5 W to 20 W.

4. A superhydrophobic graphene electric heating film, characterized in that: The superhydrophobic graphene electric heating film is prepared according to the preparation method of the superhydrophobic graphene electric heating film of claim 1; the superhydrophobic graphene electric heating film comprises an organic material substrate (1), one side of the organic material substrate (1) is distributed with a wavy micron-scale groove array structure (2) having superhydrophobicity which is etched by a laser, and the other side is covered with a conductive graphene layer (3).

5. The super-hydrophobic graphene electric heating film according to claim 4, characterized in that: The period of the micron-scale groove array structure (2) is 20 μm to 100 μm, and the height is 20 μm to 50 μm, wherein the period refers to the distance between the bottoms of adjacent grooves.

6. The super-hydrophobic graphene electric heating film according to claim 4, characterized in that: The thickness of the conductive graphene layer (3) is 20 μm to 50 μm, and the square resistance is 35 Ω / sq to 1000 Ω / sq.

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