CN117402555A - Super-hydrophobic anti-icing surface based on super-elliptic topological structure and preparation method thereof - Google Patents
Super-hydrophobic anti-icing surface based on super-elliptic topological structure and preparation method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09K3/00—Materials not provided for elsewhere
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- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
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Abstract
The invention discloses a super-hydrophobic anti-icing surface based on a super-elliptic topological structure and a preparation method thereof. The super-hydrophobic anti-icing surface comprises a super-elliptic topological structure substrate and a super-hydrophobic coating; the microstructure of the super-elliptic topological structure substrate has a protection function, and the inner super-hydrophobic coating is protected from failure caused by impact damage or friction and abrasion; the super-hydrophobic coating has an intrinsic super-hydrophobic nano structure, can reduce solid-liquid contact area and weaken solid-liquid heat transfer, thereby delaying icing, reducing ice adhesion and having anti-icing performance. The super-hydrophobic anti-icing surface has long-acting super-hydrophobicity with firm mechanical property, and the super-hydrophobic nano structure is protected by utilizing the super-elliptic topological microstructure, so that the problems of poor mechanical firmness and wear resistance of the super-hydrophobic surface are solved, the long-acting property and durability of the super-hydrophobic surface are enhanced, and the super-hydrophobic anti-icing surface can be applied to the fields of aerospace, energy sources, traffic and the like.
Description
Technical Field
The invention belongs to the field of super-hydrophobic anti-icing, and relates to a super-hydrophobic anti-icing surface based on a super-elliptic topological structure and a preparation method thereof.
Background
Under the low-temperature environment, the surface is easy to freeze, and potential safety hazards and energy efficiency losses are brought to the fields of aerospace, energy, traffic and the like. The conventional anti-icing method is environmentally friendly and has high energy consumption, and thus, a method for preparing an anti-icing surface with green color and low energy consumption is required to reduce ice formation and improve the anti-icing performance of the surface.
The biological surfaces of lotus leaves, rice leaves, butterfly wings and the like have super-hydrophobic phenomenon to natural learning, and the unique solid-gas-liquid contact interface guides the construction of novel ice-preventing and removing surfaces. The bionic super-hydrophobic surface anti-icing technology for drawing inspiration from nature is a passive anti-icing technology, and mainly reduces the surface energy or builds a micro-nano composite structure and other modes on the surface of an anti-icing area by using interface materials, reduces the contact area and contact time of liquid drops striking on the solid surface to inhibit surface icing, thereby greatly reducing the energy consumption required by anti-icing and having great engineering application prospect.
However, a great number of research results show that the low solid-liquid contact area of the superhydrophobic surface causes high local stress, so that the mechanical stability is poor, the superhydrophobic surface is easily damaged by natural weather (sun, sand and dust, wind and rain), external force (impact, friction), icing-deicing cycle and the like, finally the superhydrophobic surface is invalid, the anti-icing efficiency is reduced, and the mechanical stability becomes a key bottleneck for restricting the superhydrophobic surface in the anti-icing application field. Therefore, the mechanical fragile nano hydrophobic structure is protected by using the super elliptic topological microstructure, so that the mechanical stability of the super hydrophobic surface is improved, and the anti-icing application of the super elliptic topological microstructure in the fields of aerospace, energy, traffic and the like is expanded.
Disclosure of Invention
Aiming at the problems of poor mechanical firmness, poor durability and the like of the existing super-hydrophobic anti-icing surface, the invention adopts a substrate super-elliptic topological microstructure to protect the nano-structure strategy of the super-hydrophobic coating, regulates and controls the composition and the proportion of the organic-inorganic hybrid super-hydrophobic coating, and fills the composition and the proportion into the microstructure based on super-elliptic topology to prepare the super-hydrophobic anti-icing surface based on the super-elliptic topology. The invention discloses a series of organic-inorganic hybrid super-hydrophobic coating types, compositions and component proportions, and describes different methods for filling the super-hydrophobic coating into an ultra-elliptical microstructure in detail.
The preparation technical scheme of the invention is as follows:
the super-hydrophobic anti-icing surface based on the super-elliptic topological structure comprises a super-elliptic topological structure substrate (1) and a super-hydrophobic coating (2), wherein the microstructure of the super-elliptic topological structure substrate (1) has a protection function, and the inner super-hydrophobic coating (2) is protected from being failed due to impact damage or friction and abrasion; the super-hydrophobic coating (2) has a super-hydrophobic nano structure, can reduce solid-liquid contact area and weaken solid-liquid heat transfer, thereby delaying icing, reducing ice adhesion and having anti-icing performance.
The superhydrophobic anti-icing surface meets the following performance requirements: the water contact angle is more than 150 degrees, and the rolling angle is less than 10 degrees; after being subjected to multiple frictional wear, the surface of the material still has superhydrophobicity; compared with the surface of the original substrate, the method can prolong the icing time and reduce the ice adhesion; the surface is also anti-icing after being subjected to a plurality of frictional wear.
The super-elliptic topological structure substrate (1) is made of one of plastic, ceramic, metal and composite material, and the topological structure unit is made of one of super-elliptic shape and is manufactured by laser processing. The shape curve of the super ellipse isWherein the half diameter a, b of the super ellipse is 60-500 μm, and the index parameter n is 2-10. The value range of the adjacent super-elliptic distance is 0-100 mu m. The super-hydrophobic coating (2) is an organic-inorganic hybrid material, the organic part is one of resin polymers, the inorganic part is one of nano particles, and the organic and inorganic hybrid materials are obtained by blending an organic solvent.
The super-elliptic topological structure substrate (1) and the super-hydrophobic coating (2) are prepared by dip coating, knife coating or spray coating, and then are heated, cured and formed.
The method for preparing the super-hydrophobic anti-icing surface according to any one of the above, comprising the following steps:
step 1, processing a super-elliptic topological structure substrate (1) by processing the super-elliptic shape of the substrate according to design requirements by laser;
step 2, preparing the super-hydrophobic coating (2), namely blending organic resin and inorganic nano particles in an organic solvent, and uniformly stirring;
step 3, coating the super-hydrophobic coating (2) in the microstructure of the super-elliptic topological structure substrate (1) in a dip coating, blade coating or spray coating mode, and then heating and curing;
and 4, performing contact angle test on the prepared super-elliptic topological structure super-hydrophobic anti-icing surface, evaluating wettability, and if the super-hydrophobic requirement is not met, iterating the organic-inorganic hybridization ratio of the super-hydrophobic coating (2) in the step 2, and improving the mass ratio of the nano particles.
And 5, carrying out an anti-icing performance test on the prepared super-elliptic topological structure super-hydrophobic anti-icing surface, namely comparing the icing delay time of 10 mu l supercooled liquid drops on the super-elliptic topological structure super-hydrophobic anti-icing surface with that of an original bare substrate at the surface temperature of minus 20 ℃.
Step 6, friction test is carried out on the super-hydrophobic anti-icing surface of the prepared super-elliptic topological structure, after the surface is repeatedly rubbed for 50 times by using sand paper loaded with a weight of 500g, the contact angle of the surface is measured, and whether the super-hydrophobic requirement is still met or not; the surface icing delay time is measured and compared to the original bare substrate.
The super-hydrophobic anti-icing surface based on the super-elliptic topological structure has the beneficial effects of long-acting super-hydrophobicity and anti-icing performance with firm mechanical performance, the super-hydrophobic nano structure is protected by utilizing the super-elliptic topological microstructure, the problems of poor mechanical firmness and wear resistance of the super-hydrophobic surface are solved, the long-acting performance and durability of the super-hydrophobic surface are enhanced, the super-hydrophobic anti-icing surface still has the super-hydrophobicity and anti-icing performance of the original surface after repeated friction, and the super-hydrophobic anti-icing surface can be applied to the fields of aerospace, energy, traffic and the like.
Drawings
FIG. 1 is a schematic structural diagram of a super-hydrophobic anti-icing surface based on super-elliptical topology in examples 1, 2, and 3;
FIG. 2 is a surface topography of a superhydrophobic anti-icing surface based on a superelliptical topology as in example 1;
FIG. 3 is a graph showing the wettability of the super-hydrophobic anti-icing surface of example 1 after multiple rubs based on super-elliptic topology.
Wherein: 1-a super elliptic topological structure substrate; 2-superhydrophobic coating.
Detailed Description
The invention is further described below with reference to the drawings and detailed description.
Example 1
Super-hydrophobic anti-icing surface based on super-elliptic topological structure, as shown in fig. 1, comprises the following structures: (1) Super elliptic topological structure substrate 1 with length and width of 30mm multiplied by 30mm is made of organic glass acrylic, and the performance parameter is density of 1.19g/cm 3 Young's modulus 3.6Gpa, tensile strength 60MPa, bending strength 110MPa, melting point 130 ℃, poisson's ratio 0.4; (2) Super hydrophobic coating 2, the organic part is siloxane polymer polydimethylsiloxane and curing agent (Sylard 184, USA), inorganicThe silica nanoparticles (Desolid, R202) are used as the part, and the average particle diameter is 14nm. In fig. 1, only four pattern designs of super-elliptical structures are schematically shown, which are adjacent to each other in the vertical direction, and in actual processing, topology patterns can be repeated according to the size of the substrate and the size of the super-elliptical structures. The super-hydrophobic coating 2 is filled in the super-elliptic topological structure of the substrate. The surface topography of the super-elliptic topological structure super-hydrophobic anti-icing surface which is actually prepared is photographed by an electron scanning microscope, and the structure is shown in figure 2.
The preparation method comprises the following steps:
step 1, processing a super-ellipse shape on an organic glass acrylic substrate by laser, wherein the half diameter a and the half diameter b of the super-ellipse are 250 mu m, the index n is 3, and the adjacent distance d is 25 mu m;
step 2, polydimethylsiloxane, a curing agent and silicon dioxide nano particles are mixed in a normal hexane solvent according to a mass ratio of 7:0.7:3, mixing and stirring uniformly;
step 3, the super-hydrophobic coating is coated in the microstructure of the super-elliptic topological structure substrate by scraping, then placed in a vacuum tank for 10 minutes, and repeated for 2-3 times until the super-hydrophobic coating fills the super-elliptic topological microstructure, and then cured for 2 hours at 80 ℃;
and 4, carrying out contact angle test on the super-hydrophobic surface with the super-elliptic topological structure, wherein the water contact angle is 155 degrees, the rolling angle is 5 degrees, and the super-hydrophobic requirement is met.
And 5, carrying out an anti-icing performance test on the prepared super-elliptic topological structure super-hydrophobic anti-icing surface, namely delaying the icing time of 10 mu l supercooled liquid drops on the super-elliptic topological structure super-hydrophobic anti-icing surface by more than 20 times compared with the original bare acrylic surface when the surface temperature is minus 20 ℃.
And 6, repeatedly rubbing the super-elliptic super-hydrophobic surface by using sand paper loaded with a weight of 500g, wherein the single rubbing distance is 2cm, and the water contact angle of the super-elliptic topological structure super-hydrophobic surface after 50 times of rubbing is 151 degrees, and the rolling angle is 8 degrees, so that the super-hydrophobic requirement is still met as shown in figure 3. And the icing time is delayed by more than 15 times compared with the original bare acrylic surface.
Example 2
Super-elliptic topologyThe superhydrophobic anti-icing surface of the structure, as shown in fig. 1, comprises: (1) Super elliptic topological structure substrate with length and width of 30mm multiplied by 30mm and organic glass acrylic material, and its performance parameter is density of 1.19g/cm 3 Young's modulus 3.6Gpa, tensile strength 60MPa, bending strength 110MPa, melting point 130 ℃, poisson's ratio 0.4; (2) The super-hydrophobic coating has an organic part of a siloxane polymer polydimethylsiloxane (Sylard 184, dow Corning, USA) and an inorganic part of silica nanoparticles (Desoxel, R202), and has a hydrophobic average particle size of 14nm.
The preparation method comprises the following steps:
step 1, processing a super-ellipse shape on an organic glass acrylic substrate by laser, wherein the half diameters a and b of the super-ellipse are 250 mu m, the index n is 3, and the adjacent distance d is 75 mu m;
step 2, the silicone polymer polydimethylsiloxane and the silicon dioxide nano particles are mixed in a normal hexane solvent according to a mass ratio of 7:0.7:3, mixing and stirring uniformly;
step 3, spraying the super-hydrophobic coating into the microstructure of the super-elliptic topological structure substrate under the pressure of 0.1MPa, wherein the distance between a substrate and a nozzle is 20cm during spraying, spraying for 2 times, and then curing for 2 hours at 80 ℃;
step 4, carrying out contact angle test on the prepared super-elliptic topological structure super-hydrophobic surface, wherein the water contact angle is 145 degrees, the organic-inorganic hybridization ratio of the super-hydrophobic coating 2 in the step 2 is iterated without meeting the super-hydrophobic requirement, and the mass ratio of the nano particles is increased to 7:0.7:3.5, carrying out contact angle test, wherein the water contact angle is 153 degrees, the rolling angle is 5 degrees, and the superhydrophobic requirement is met;
step 5, carrying out an anti-icing performance test on the prepared super-hydrophobic anti-icing surface with the super-elliptic topological structure, namely delaying the icing time of 10 mu l supercooled liquid drops on the super-hydrophobic anti-icing surface by more than 16 times compared with the original exposed acrylic surface when the surface temperature is minus 20 ℃;
step 6, repeatedly rubbing the super-elliptic super-hydrophobic surface by using sand paper loaded with 500g of weight, wherein the single rubbing distance is 2cm, the water contact angle of the super-elliptic topological structure super-hydrophobic surface after rubbing for 50 times is 150 degrees, the rolling angle is 10 degrees, and the super-hydrophobic requirement is still met; the icing time is delayed by more than 10 times compared with the original bare acrylic surface.
Example 3
Super-hydrophobic anti-icing surface based on super-elliptic topological structure, as shown in fig. 1, comprises the following structures: (1) The super elliptic topological structure substrate has the length and width of 300mm multiplied by 300mm, is made of metal aluminum alloy, and has the following performance parameters: density 2.81g/cm 3 Young's modulus 71.7GPa, tensile strength 572MPa, flexural strength 385MPa, poisson's ratio 0.33; (2) The super-hydrophobic coating comprises an organic part of epoxy resin E-51 and a curing agent T-31 (Hangzhou five-party harbor adhesive Co., ltd.) and an inorganic part of carbon nano-particles with an average particle size of 20nm.
The preparation method comprises the following steps:
step 1, processing a super-ellipse shape on an aluminum alloy substrate by laser, wherein the half diameters a and b of the super-ellipse are 250 mu m, the index n is 8, and the adjacent distance d is 25 mu m;
step 2, epoxy resin E-51, curing agent T-31 and carbon nano particles are mixed in acetone solvent according to the following ratio of 7:3.5:3, mixing and stirring uniformly;
step 3, spraying the super-hydrophobic coating into the microstructure of the super-elliptic topological structure substrate under the pressure of 0.1MPa, wherein the distance between a substrate and a nozzle is 20cm during spraying, spraying for 2 times, and then curing for 2 hours at 60 ℃;
and 4, carrying out contact angle test on the super-hydrophobic surface with the super-elliptic topological structure, wherein the water contact angle is 156 degrees, the rolling angle is 2 degrees, and the super-hydrophobic requirement is met.
And 5, carrying out an anti-icing performance test on the prepared super-elliptic topological structure super-hydrophobic anti-icing surface, namely delaying the icing time of 10 mu l supercooled liquid drops on the super-elliptic topological structure super-hydrophobic anti-icing surface by more than 22 times compared with the original bare acrylic surface when the surface temperature is minus 20 ℃.
Step 6, repeatedly rubbing the super-elliptic super-hydrophobic surface by using sand paper loaded with 500g of weight, wherein the single rubbing distance is 2cm, and the water contact angle of the super-elliptic topological structure super-hydrophobic surface after rubbing for 50 times is 152 degrees, the rolling angle is 7 degrees, so that the super-hydrophobic requirement is still met; the icing time is delayed by more than 15 times compared with the original bare acrylic surface.
It should be noted that, according to the above embodiments of the present invention, those skilled in the art can fully realize the full scope of the independent claims and the dependent claims, and the implementation process and method are the same as those of the above embodiments; and not specifically described in part are well known in the art. While the invention has been described with respect to certain preferred embodiments, it will be apparent to those skilled in the art that various changes and substitutions can be made herein without departing from the scope of the invention as defined by the appended claims.
Claims (9)
1. The super-hydrophobic anti-icing surface based on the super-elliptic topological structure is characterized by comprising a super-elliptic topological structure substrate (1) and a super-hydrophobic coating (2), wherein the microstructure of the super-elliptic topological structure substrate (1) has a protection function, and the inner super-hydrophobic coating (2) is protected from failure caused by impact damage or friction and abrasion; the super-hydrophobic coating (2) has an intrinsic super-hydrophobic nano structure, can reduce solid-liquid contact area and weaken solid-liquid heat transfer, thereby delaying icing, reducing ice adhesion and having anti-icing performance.
2. The superhydrophobic anti-icing surface according to claim 1, wherein the superhydrophobic anti-icing surface meets the following superhydrophobic performance requirements: the water contact angle is greater than 150 deg. and the rolling angle is less than 10 deg..
3. The superhydrophobic anti-icing surface according to claim 1, wherein the superhydrophobic anti-icing surface has superhydrophobic surface after being subjected to a plurality of frictional wear.
4. The superhydrophobic anti-icing surface according to claim 1, wherein the superhydrophobic anti-icing surface is capable of extending icing time and reducing ice adhesion relative to an original substrate surface.
5. The superhydrophobic anti-icing surface according to claim 1, wherein the superhydrophobic anti-icing surface has anti-icing properties after being subjected to a plurality of frictional wear.
6. The superhydrophobic anti-icing surface according to claim 1, characterized in that the material of the superelliptical topological substrate (1) is one of plastic, ceramic, metal and composite material, and the topological unit is one of superelliptical shape, made by laser machining.
7. The superhydrophobic anti-icing surface according to claim 1, wherein said superhydrophobic coating (2) is an organic-inorganic hybrid material, the organic fraction is one of resin polymers, the inorganic fraction is one of nanoparticles, both obtained by blending with an organic solvent; preferably, the resin polymer is polydimethylsiloxane or epoxy resin; preferably, the nano-particles are nano-silica or carbon nano-particles; preferably, the particle size of the nano particles is 1-30 nm.
8. The super-hydrophobic anti-icing surface according to claim 1, characterized in that the super-elliptic topological structure substrate (1) and the super-hydrophobic coating (2) are prepared by dip coating, knife coating or spray coating, and then are formed by heating and curing.
9. A method of preparing a superhydrophobic anti-icing surface according to any of claims 1-8 comprising the steps of:
step 1, processing a super-elliptic topological structure substrate (1), namely processing the super-elliptic shape of the substrate by laser according to design requirements, and then cleaning the surface;
step 2, preparing the super-hydrophobic coating (2), namely blending organic resin and inorganic nano particles in an organic solvent, and uniformly stirring;
step 3, coating the super-hydrophobic coating (2) in the microstructure of the super-elliptic topological structure substrate (1) in a dip coating, blade coating or spray coating mode, and then heating and curing;
step 4, performing contact angle test on the prepared super-elliptic topological structure super-hydrophobic anti-icing surface, evaluating wettability of the super-elliptic topological structure super-hydrophobic anti-icing surface, and if the super-elliptic topological structure super-hydrophobic requirement is not met, iterating the organic-inorganic hybridization ratio of the super-hydrophobic coating (2) in the step 2;
step 5, carrying out an anti-icing performance test on the prepared super-elliptic topological structure super-hydrophobic anti-icing surface, namely comparing the icing delay time of 10 mu l supercooled liquid drops on the super-elliptic topological structure super-hydrophobic anti-icing surface with that of an original bare substrate at the surface temperature of minus 20 ℃;
step 6, friction test is carried out on the super-hydrophobic anti-icing surface of the prepared super-elliptic topological structure, after the surface is repeatedly rubbed for 100 times by using sand paper loaded with a weight of 500g, the contact angle of the surface is measured, and whether the super-hydrophobic requirement is still met or not; the surface icing delay time is measured and compared to the original bare substrate.
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