Polymer modified surface with ice-repellent effect and its preparation method and application

Abstract

A polymer-modified surface with anti-icing properties, its preparation method, and its application belong to the field of surface engineering technology. The preparation method of this polymer-modified surface with anti-icing properties includes the following steps: S1, hydroxylating and activating the surface of a substrate material, followed by immersion in an initiator monolayer assembly solution to complete surface self-assembly; the initiator monomolecule has surface anchoring groups and initiating groups; S2, immersing the self-assembled substrate material in a reaction system containing a hygroscopic polymer monomer, a catalyst, and ligands for polymerization, forming a hygroscopic polymer brush layer on the substrate material, thus obtaining a polymer-modified surface with anti-icing properties. This invention has advantages such as excellent anti-icing properties, broad substrate applicability, high interfacial stability, and resistance to lubrication layer loss.

Description

Technical Field

[0001] This invention relates to a polymer-modified surface with anti-icing properties, its preparation method and application, belonging to the field of surface engineering technology. Background Technology

[0002] Icing is a widespread phenomenon in nature and in modern engineering service environments, and excessive accumulation of ice and snow is often extremely destructive. For example, in critical infrastructure sectors such as power transmission, aerospace, wind power generation, and transportation, icing under extreme weather conditions can lead to power grid paralysis (e.g., damage to aluminum conductors and steel towers), pitot tube failure, loss of lift for aircraft (e.g., icing of metal skins or optical windshields), or a sharp decline in the aerodynamic performance of wind turbine blades (e.g., icing of carbon fiber / glass fiber composite materials), causing severe economic losses and even catastrophic accidents. Therefore, developing efficient anti-icing technologies that can be widely applied to the aforementioned complex material substrates is an urgent need to address the challenges of extreme climates and ensure the safe and stable operation of major engineering projects.

[0003] Currently, anti-icing strategies are mainly divided into two categories: active anti-icing and passive anti-icing. Traditional active anti-icing technologies, such as electrothermal, gas-thermal, and chemical agents, can remove ice to some extent, but they generally have significant limitations, including high energy consumption, complex systems, environmental pollution, and potential damage to the equipment substrate. In contrast, passive anti-icing technologies rely on the intrinsic physical or chemical properties of the material surface to delay icing and reduce ice adhesion, and have become a current research hotspot due to their advantages such as low carbon footprint and zero energy consumption.

[0004] In existing passive anti-icing technologies, superhydrophobic surfaces and lubricant-injected porous surfaces are two representative systems. However, under harsh, extreme cooling and high humidity conditions, these existing technologies all exhibit insurmountable technical bottlenecks:

[0005] First, in supercooled and humid environments, condensate droplets can easily penetrate the microscopic defects of superhydrophobic surfaces and nucleate and freeze in situ, triggering a severe "mechanical interlocking" effect. This causes the ice adhesion strength at the interface to increase exponentially, resulting in the complete failure of the anti-icing function. Second, for lubricated surfaces, the free lubricant injected inside usually exists only through physical adsorption. Under long-term airflow shearing, rainwater erosion, or repeated freezing-de-icing cycles, the lubricant is prone to irreversible loss, leading to a rapid decline in anti-icing performance. Summary of the Invention

[0006] To address the aforementioned shortcomings of existing technologies, this invention proposes a polymer-modified surface with anti-icing properties, its preparation method, and its application. This surface possesses advantages such as excellent anti-icing properties, broad substrate compatibility, high interfacial stability, and resistance to lubrication layer loss.

[0007] The first aspect of this invention relates to a method for preparing a polymer-modified surface with anti-icing properties, comprising the following steps:

[0008] S1, the surface of the substrate material is activated by hydroxylation, and then immersed in an initiator monolayer assembly solution to complete surface self-assembly; the initiator monolayer has surface anchoring groups and initiating groups;

[0009] S2, the substrate material that has completed surface self-assembly is immersed in a reaction system containing hygroscopic polymer monomers, catalysts and ligands to carry out a polymerization reaction, forming a hygroscopic polymer brush layer on the substrate material, and obtaining a polymer-modified surface with anti-icing performance.

[0010] The substrate material is a metallic material, an inorganic non-metallic material, a polymer material, or a composite material thereof;

[0011] The hygroscopic polymer monomer is at least one of oligoethylene glycol monomers, zwitterionic monomers, methacrylate monomers, and methacrylamide monomers.

[0012] The second aspect of the present invention relates to a polymer-modified surface with anti-icing properties, which is prepared by the above method.

[0013] The third aspect of the present invention relates to the application of the above-mentioned polymer-modified surfaces with anti-icing properties in anti-icing environments.

[0014] Technical effect

[0015] In this invention, the polymer-modified surface with anti-icing properties is composed of a moisture-absorbing polymer brush layer. The moisture-absorbing polymer brush layer can spontaneously capture moisture from the supercooled and high-humidity environment and form a "quasi-liquid hydration layer" that is extremely difficult to freeze in situ at the solid-ice interface, thereby providing molecular-level interfacial lubrication and effectively preventing ice crystals from directly adhering to the substrate.

[0016] The moisture-absorbing polymer brush layer in this invention is covalently grafted onto a hydroxylated activated substrate material through a surface-initiated atom transfer radical polymerization reaction. The substrate material has strong versatility, high interface stability, excellent and long-lasting interface lubrication, and the resulting anti-icing effect is superior and durable. Detailed Implementation

[0017] The following is a detailed description of the embodiments of the present invention. Experimental methods not specifically described in the embodiments were performed according to conventional methods and conditions.

[0018] This invention relates to a polymer-modified surface with anti-icing properties, and the specific preparation method of this surface includes the following steps:

[0019] S1, the surface of the substrate material is activated by hydroxylation, and then immersed in an initiator monolayer assembly solution to complete surface self-assembly; the initiator monolayer has surface anchoring groups and initiating groups;

[0020] S2, the substrate material that has completed surface self-assembly is immersed in a reaction system containing hygroscopic polymer monomers, catalysts and ligands to carry out a polymerization reaction, forming a hygroscopic polymer brush layer on the substrate material, and obtaining a polymer-modified surface with anti-icing performance.

[0021] The substrate material is a metallic material, an inorganic non-metallic material, a polymer material, or a composite material thereof;

[0022] The hygroscopic polymer monomer is at least one of oligoethylene glycol monomers, zwitterionic monomers, methacrylate monomers, and methacrylamide monomers.

[0023] In some preferred embodiments, the molar ratio of the hygroscopic polymer monomer, catalyst, and ligand is 100–2000:1:1–3; more preferably, the molar ratio of the hygroscopic polymer monomer, catalyst, and ligand is 100–500:1:1–2.

[0024] In some preferred embodiments, the moisture-absorbing polymer monomer is at least one of oligoethylene glycol alkyl ether acrylate, polyethylene glycol methacrylate, sulfobetaine methacrylate, carboxybetaine methacrylate, 2-methacryloyloxyethyl phosphocholine, hydroxyethyl methacrylate, and N,N-dimethylacrylamide.

[0025] In some preferred embodiments, the catalyst is cuprous bromide or cuprous chloride;

[0026] In some preferred embodiments, the ligand is one of pentamethyldiethylenetriamine, 2,2'-bipyridine, or tris(2-dimethylaminoethyl)amine.

[0027] In some preferred embodiments, the substrate material is a foil, a tube, a mesh component, or a three-dimensional component.

[0028] In some preferred embodiments, the metallic material is selected from one of titanium, titanium alloy, aluminum, aluminum alloy, iron, steel, stainless steel, copper alloy, and magnesium alloy.

[0029] In some preferred embodiments, the inorganic non-metallic material is selected from one of glass, quartz, silicon wafers, and ceramics.

[0030] In some preferred embodiments, the polymer material is selected from polyurethane and epoxy resin.

[0031] In some preferred embodiments, the composite material is selected from glass fiber composite material and carbon fiber composite material.

[0032] In some preferred embodiments, the hydroxylation activation treatment is at least one of oxygen plasma treatment, ultraviolet-ozone treatment, strong acid etching treatment, strong alkali etching treatment, and strong chemical oxidation treatment.

[0033] In some preferred embodiments, the surface anchoring group of the initiator monomolecule is selected from one of phosphonic acid group, siloxane group, carboxyl group, and catechol group, and the initiating group of the initiator monomolecule is one of one of brominated alkyl terminal group, chloroalkyl terminal group, brominated ester terminal group, and chloroester terminal group.

[0034] In some preferred embodiments, the initiator monolayer assembly solution comprises an initiator monomolecule and an inert diluent molecule, with a molar ratio of 1:9 to 9:1.

[0035] In some preferred embodiments, the inert diluent molecule is a saturated straight-chain alkyl monophosphonic acid or a saturated branched alkyl monophosphonic acid; more preferably, at least one of C1-C20 saturated straight-chain alkylphosphonic acid, C4-C18 branched alkylphosphonic acid, and perfluorinated saturated alkylphosphonic acid is used.

[0036] In some preferred embodiments, the reaction system includes a solvent, wherein the solvent is at least one selected from tetrahydrofuran, water, methanol, ethanol, and N,N-dimethylformamide.

[0037] In some preferred embodiments, the polymerization reaction is carried out under a non-oxidizing atmosphere at a temperature of 20–90°C for a reaction time of 1–48 h. More preferably, the reaction temperature is 30–70°C for a reaction time of 6–24 h.

[0038] Example 1

[0039] The process for preparing the polymer-modified surface with anti-icing properties in this embodiment is as follows:

[0040] Pretreatment: The substrate material, commercial pure titanium foil, is polished and cleaned, followed by oxygen plasma treatment for 5 minutes for surface activation;

[0041] Initiator modification: The activated pure titanium foil was immersed in a 5 mM initiator monolayer assembly solution (solvent was ethanol, active initiator was 11-(2-bromo-2-methylpropionyloxy)undecylphosphonic acid, inert diluent was 1-tetradecylphosphonic acid, and the molar ratio of active initiator to inert diluent was 1:1) and self-assembled at room temperature in the dark for 24 h; then it was taken out, rinsed with anhydrous ethanol and dried with nitrogen to obtain a pure titanium foil with an initiator monolayer fixed on the surface.

[0042] Preparation of the reaction system (containing hygroscopic polymer monomer): In an anhydrous and oxygen-free environment, 43.0 g of the hygroscopic monomer oligoethylene glycol alkyl ether acrylate (8.9 × 10⁻⁶ g) was added. -2 Add mol) to a mixed solution containing tetrahydrofuran (50.0 mL), the catalyst cuprous bromide (120.0 mg), and the ligand pentamethyldiethylenetriamine (0.32 mL), and stir vigorously until homogeneous;

[0043] Polymerization: Pure titanium foil with an initiator monolayer fixed on its surface was completely immersed in a reaction system containing hygroscopic polymer monomers, sealed and placed in a constant temperature oil bath at 60°C to initiate surface atom transfer radical polymerization for 12 hours. After the reaction was completed, the sample was taken out and ultrasonically washed with tetrahydrofuran and deionized water in sequence to fully remove surface residues. It was then placed in a vacuum drying oven at 60°C to dry and remove solvent, thus obtaining a hygroscopic polymer-modified anti-icing surface.

[0044] Example 2

[0045] The process for preparing the polymer-modified surface with anti-icing properties in this embodiment is as follows:

[0046] Pretreatment: The substrate material, commercial pure titanium foil, is polished and cleaned, followed by oxygen plasma treatment for 5 minutes for surface activation;

[0047] Initiator modification: The activated pure titanium foil was immersed in a 5 mM initiator monolayer assembly solution (solvent was ethanol, active initiator was 11-(2-bromo-2-methylpropionyloxy)undecylphosphonic acid, inert diluent was 1-tetradecylphosphonic acid, and the molar ratio of active initiator to inert diluent was 1:1) and self-assembled at room temperature in the dark for 24 h; then it was taken out, rinsed with anhydrous ethanol and dried with nitrogen to obtain a pure titanium foil with an initiator monolayer fixed on the surface.

[0048] Reaction system configuration: In an anhydrous and oxygen-free environment, 43.0 g of hygroscopic monomer oligoethylene glycol alkyl ether acrylate (8.9 × 10⁻⁶ g) was added. -2 Add mol) to a mixed solution containing tetrahydrofuran (50.0 mL), the catalyst cuprous bromide (120.0 mg), and the ligand pentamethyldiethylenetriamine (0.32 mL), and stir vigorously until homogeneous;

[0049] Polymerization: Pure titanium foil with an initiator monolayer fixed on its surface was completely immersed in a reaction system containing hygroscopic polymer monomers, sealed and placed in a 60°C constant temperature oil bath to initiate surface atom transfer radical polymerization for 24 hours. After the reaction was completed, the sample was taken out and ultrasonically washed with tetrahydrofuran and deionized water in sequence to fully remove surface residues. It was then placed in a 60°C vacuum drying oven to dry and remove solvent, thus obtaining a hygroscopic polymer-modified anti-ice surface.

[0050] Example 3

[0051] The process for preparing the polymer-modified surface with anti-icing properties in this embodiment is as follows:

[0052] Pretreatment: The substrate material, commercial pure titanium foil, is polished and cleaned, followed by oxygen plasma treatment for 5 minutes for surface activation;

[0053] Initiator modification: The activated pure titanium foil was immersed in a 5 mM initiator monolayer assembly solution (solvent was ethanol, active initiator was 11-(2-bromo-2-methylpropionyloxy)undecylphosphonic acid, inert diluent was 1-tetradecylphosphonic acid, and the molar ratio of active initiator to inert diluent was 1:1) and self-assembled at room temperature in the dark for 24 h; then it was taken out, rinsed with anhydrous ethanol and dried with nitrogen to obtain a pure titanium foil with an initiator monolayer fixed on the surface.

[0054] Reaction system configuration: In an anhydrous and oxygen-free environment, 43.0 g of hygroscopic monomer oligoethylene glycol alkyl ether acrylate (8.9 × 10⁻⁶ g) was added. -2 Add mol) to a mixed solution containing tetrahydrofuran (50.0 mL), the catalyst cuprous bromide (120.0 mg), and the ligand pentamethyldiethylenetriamine (0.32 mL), and stir vigorously until homogeneous;

[0055] Polymerization: Pure titanium foil with an initiator monolayer fixed on its surface was completely immersed in a reaction system containing hygroscopic polymer monomers, sealed and placed in a constant temperature oil bath at 50°C to initiate surface atom transfer radical polymerization for 12 hours. After the reaction was completed, the sample was taken out and ultrasonically washed with tetrahydrofuran and deionized water in sequence to fully remove surface residues. It was then placed in a vacuum drying oven at 60°C to dry and remove solvent, thus obtaining a hygroscopic polymer-modified anti-icing surface.

[0056] Example 4

[0057] The process for preparing the polymer-modified surface with anti-icing properties in this embodiment is as follows:

[0058] Pretreatment: The substrate material, commercial pure titanium foil, is polished and cleaned, followed by oxygen plasma treatment for 5 minutes for surface activation;

[0059] Initiator modification: The activated pure titanium foil was immersed in a 5 mM initiator monolayer assembly solution (solvent was ethanol, active initiator was 11-(2-bromo-2-methylpropionyloxy)undecylphosphonic acid, inert diluent was 1-tetradecylphosphonic acid, and the molar ratio of active initiator to inert diluent was 1:1) and self-assembled at room temperature in the dark for 24 h; then it was taken out, rinsed with anhydrous ethanol and dried with nitrogen to obtain a pure titanium foil with an initiator monolayer fixed on the surface.

[0060] Reaction system configuration: Under a nitrogen atmosphere, 43.0 g of hygroscopic monomer oligoethylene glycol alkyl ether acrylate (8.9 × 10⁻⁶ g) was added. -2 Add mol) to 50.0 mL of green mixed solvent (deionized water and methanol volume ratio 1:1), then add the catalyst cuprous bromide (120.0 mg) and the ligand 2,2'-bipyridine (0.32 mL), and stir vigorously until homogeneous;

[0061] Polymerization: Pure titanium foil with an initiator monolayer fixed on its surface was completely immersed in a reaction system containing hygroscopic polymer monomers, sealed and placed in a constant temperature oil bath at 30°C to initiate surface atom transfer radical polymerization for 12 hours. After the reaction was completed, the sample was taken out and ultrasonically washed with tetrahydrofuran and deionized water in sequence to fully remove surface residues. It was then placed in a vacuum drying oven at 60°C to dry and remove solvent, thus obtaining a hygroscopic polymer-modified anti-icing surface.

[0062] Example 5

[0063] The process for preparing the polymer-modified surface with anti-icing properties in this embodiment is as follows:

[0064] Pretreatment: Grind and clean the TC4 titanium alloy (commonly used in aerospace) porous mesh component as the substrate material, and then perform surface activation by UV-ozone treatment for 30 minutes;

[0065] Initiator modification: The activated TC4 titanium alloy porous mesh component was immersed in a 5 mM initiator monolayer assembly solution (solvent was ethanol, active initiator was 11-(2-bromo-2-methylpropionyloxy)undecylphosphonic acid, inert diluent was 1-tetradecylphosphonic acid, and the molar ratio of active initiator to inert diluent was 1:1) and self-assembled at room temperature in the dark for 24 h; then it was taken out, rinsed with anhydrous ethanol and dried with nitrogen to obtain a TC4 titanium alloy porous mesh component with an initiator monolayer fixed on the surface;

[0066] Reaction system configuration: In an anhydrous and oxygen-free environment, 43.0 g of hygroscopic monomer oligoethylene glycol alkyl ether acrylate (8.9 × 10⁻⁶ g) was added. -2 Add mol) to a mixed solution containing tetrahydrofuran (50.0 mL), the catalyst cuprous bromide (120.0 mg), and the ligand pentamethyldiethylenetriamine (0.32 mL), and stir vigorously until homogeneous;

[0067] Polymerization: A porous mesh component of TC4 titanium alloy with an initiator monolayer fixed on its surface was completely immersed in a reaction system containing hygroscopic polymer monomers, sealed and placed in a constant temperature oil bath at 70°C to initiate surface atom transfer radical polymerization for 24 hours. After the reaction was completed, the sample was taken out and ultrasonically washed with tetrahydrofuran and deionized water in sequence to fully remove surface residues. It was then placed in a vacuum drying oven at 60°C to dry and remove solvent, thus obtaining a hygroscopic polymer-modified anti-icing surface.

[0068] Example 6

[0069] The process for preparing the polymer-modified surface with anti-icing properties in this embodiment is as follows:

[0070] Pretreatment: Grind and clean the substrate material 7075 aluminum alloy (commonly used in aerospace) foil, then immerse it in 5wt% NaOH solution and 10vol% HNO3 solution in turn to remove surface oil stains, then wash with deionized water and dry, and then treat with oxygen plasma for 5 minutes for surface activation.

[0071] Initiator modification: The activated 7075 aluminum alloy foil was immersed in a 5 mM initiator monolayer assembly solution (solvent was ethanol, active initiator was 11-(2-bromo-2-methylpropionyloxy)undecylphosphonic acid, inert diluent was 1-tetradecylphosphonic acid, and the molar ratio of active initiator to inert diluent was 1:1) and self-assembled at room temperature in the dark for 24 h; then it was taken out, rinsed with anhydrous ethanol and dried with nitrogen to obtain 7075 aluminum alloy foil with an initiator monolayer fixed on the surface.

[0072] Reaction system configuration: In an anhydrous and oxygen-free environment, 43.0 g of hygroscopic monomer oligoethylene glycol alkyl ether acrylate (8.9 × 10⁻⁶ g) was added. -2 Add mol) to a mixed solution containing tetrahydrofuran (50.0 mL), the catalyst cuprous bromide (120.0 mg), and the ligand pentamethyldiethylenetriamine (0.32 mL), and stir vigorously until homogeneous;

[0073] Polymerization: A 7075 aluminum alloy foil with an initiator monolayer fixed on its surface was completely immersed in a reaction system containing hygroscopic polymer monomers, sealed and placed in a 60°C constant temperature oil bath to initiate surface atom transfer radical polymerization for 12 hours. After the reaction was completed, the sample was taken out and ultrasonically washed with tetrahydrofuran and deionized water in sequence to fully remove surface residues. It was then placed in a 60°C vacuum drying oven to dry and remove solvent, thus obtaining a hygroscopic polymer-modified anti-icing surface.

[0074] Example 7

[0075] The process for preparing the polymer-modified surface with anti-icing properties in this embodiment is as follows:

[0076] Pretreatment: The substrate material commercial glass slide (quartz glass) was ultrasonically cleaned in sequence with acetone, ethanol and deionized water. Then it was completely immersed in piranha washing solution (a mixed solution of concentrated sulfuric acid and 30% hydrogen peroxide in a volume ratio of 3:1) and heated at 80°C for 1 hour for surface activation treatment (strong oxidation and hydroxylation). After that, it was rinsed with a large amount of deionized water and dried with nitrogen.

[0077] Initiator modification: The activated glass slide was immersed in an anhydrous toluene solution of 5% (v / v) bromoisobutyramidopropyltriethoxysilane and self-assembled at room temperature in the dark for 24 h; then it was taken out, rinsed with toluene and ethanol in sequence and dried to obtain a glass slide with an initiator covalently grafted on the surface.

[0078] Reaction system configuration: In an anhydrous and oxygen-free environment, 43.0 g of hygroscopic monomer oligoethylene glycol alkyl ether acrylate (8.9 × 10⁻⁶ g) was added. -2 Add mol) to a mixed solution containing tetrahydrofuran (50.0 mL), the catalyst cuprous bromide (120.0 mg), and the ligand pentamethyldiethylenetriamine (0.32 mL), and stir vigorously until homogeneous;

[0079] Polymerization: A glass slide with an initiator monolayer fixed on its surface is completely immersed in a reaction system containing hygroscopic polymer monomers, sealed and placed in a constant temperature oil bath at 60°C to initiate surface atom transfer radical polymerization for 12 hours. After the reaction is complete, the sample is taken out and ultrasonically washed with tetrahydrofuran and deionized water in sequence to fully remove surface residues. It is then placed in a vacuum drying oven at 60°C to dry and remove solvent, thus obtaining a hygroscopic polymer-modified anti-icing surface.

[0080] Example 8

[0081] The process for preparing the polymer-modified surface with anti-icing properties in this embodiment is as follows:

[0082] Pretreatment: The substrate material, sheet carbon fiber composite, was polished, cleaned, and dried. It was then immersed in a buffer solution of 10 mM tris(hydroxymethyl)aminomethane and hydrochloric acid (pH=8.5, containing 2 mg / mL dopamine hydrochloride) and reacted at room temperature under aerobic conditions for 24 h to achieve surface activation (forming a strong polydopamine-rich active group coating). After the reaction was completed, it was thoroughly rinsed with deionized water.

[0083] Initiator modification: The activated sheet carbon fiber composite material was placed in an anhydrous tetrahydrofuran solution with a triethylamine concentration of 0.1 mL / L. 5 mL of an anhydrous tetrahydrofuran solution with a α-bromoisobutyryl bromide concentration of 5 mL / L was slowly added dropwise under ice-water bath conditions. After the addition was completed within half an hour, the mixture was transferred to room temperature and reacted for 12 h to allow the initiating groups to be covalently grafted onto the amino or hydroxyl groups of the coating. After the reaction was completed, the mixture was washed with a large amount of organic solvent and dried to obtain a sheet carbon fiber composite material with an initiator monolayer fixed on the surface.

[0084] Reaction system configuration: In an anhydrous and oxygen-free environment, 43.0 g of hygroscopic monomer oligoethylene glycol alkyl ether acrylate (8.9 × 10⁻⁶ g) was added. -2 Add mol) to a mixed solution containing tetrahydrofuran (50.0 mL), the catalyst cuprous bromide (120.0 mg), and the ligand pentamethyldiethylenetriamine (0.32 mL), and stir vigorously until homogeneous;

[0085] Polymerization: The sheet-like carbon fiber composite material with an initiator monolayer fixed on its surface was completely immersed in a reaction system containing hygroscopic polymer monomers, sealed and placed in a constant temperature oil bath at 60°C to initiate surface atom transfer radical polymerization for 12 hours. After the reaction was completed, the sample was taken out and ultrasonically washed with tetrahydrofuran and deionized water in sequence to fully remove surface residues. It was then placed in a vacuum drying oven at 60°C to dry and remove solvent, thus obtaining a hygroscopic polymer-modified anti-ice surface.

[0086] test

[0087] The anti-icing effect and interface stability of the above embodiments were tested. The test method is as follows, and the results are shown in Table 1 (Comparative Example 1 is an untreated commercial pure titanium foil).

[0088] 1. Ice Adhesion Strength Test: In a high-humidity, cold environment with a relative humidity of 70%, a 10mm inner diameter plastic cylindrical mold was placed on the sample surface and deionized water was injected. The ambient temperature was then lowered to -15℃ and kept at this constant temperature for 3 hours to allow the droplets to completely freeze. Using a high-precision push-pull force gauge, the bottom of the ice column was pushed at a constant speed of 1mm / s, and the maximum shear force (F) when the ice column detached from the surface was recorded. The ice adhesion strength (τ=F / A) was calculated based on the bottom area (A). Surfaces with an ice adhesion strength below 100kPa are generally considered to have excellent low ice adhesion (i.e., passive de-icing) characteristics.

[0089] 2. Freezing Delay Time Test: The sample was placed in a self-made condensation chamber equipped with a semiconductor cooling stage. The surface temperature was set and maintained at -15℃, and the ambient relative humidity was maintained at a supercooled high-humidity state of 80%. 10μL of deionized water was dropped onto the sample surface, and the state changes of the water droplet were recorded in real time using a high-definition camera. The time elapsed from the moment the water droplet touched the cold surface until the water droplet completely lost its transparency (i.e., completely froze into ice) was recorded as the freezing delay time; the longer the time, the better the anti-icing performance.

[0090] 3. Cyclic De-icing Durability Test: The sample was subjected to a continuous "ice-ice removal" cycle test; after each removal, water was dripped and frozen again at the same location and the ice adhesion strength was measured. The change in ice adhesion strength after 200 complete cycles was recorded to evaluate the interfacial stability of the hydration layer under repeated mechanical shearing.

[0091] Table 1 Icing delay time (min) Initial ice adhesion strength (kPa) Ice adhesion strength (kPa) after 200 de-icing cycles Comparative Example 1 <1 350±85 >1500 Example 1 125 18±3 22±4 Example 2 140 15±2 18±3 Example 3 105 25±4 32±5 Example 4 160 9±2 12±2 Example 5 115 22±4 28±5 Example 6 120 20±3 25±4 Example 7 130 16±2 20±3 Example 8 110 26±5 35±6

[0092] Comparative Example 1 was an untreated pure titanium foil sheet, which was extremely prone to icing and exhibited severe mechanical interlocking, resulting in surface damage after 200 de-icing cycles. Compared to Comparative Example 1, Example 1, after surface modification treatment, demonstrated excellent anti-icing performance and superior durability. Compared to Example 1, Example 2 extended the reaction time, further improving anti-icing and durability. Compared to Example 1, Example 3 lowered the reaction temperature while still maintaining excellent anti-icing effects. Compared to Example 1, Example 4 adjusted the type of hygroscopic polymer monomer, using a zwitterionic monomer, resulting in a very strong hydration layer and exhibiting superior extremely low ice adhesion and anti-icing performance. Example 5 demonstrated the effectiveness of the method of the present invention for... Commercial alloys and complex three-dimensional structures have good versatility; Example 6, based on the strong coordination bond between the natural alumina layer and phosphonic acid groups, has anti-icing performance and durability comparable to titanium substrates, demonstrating excellent applicability in aerospace light alloys; Example 7, the glass slide is covalently anchored by a silane initiator, resulting in dense and uniform grafting, excellent and durable anti-icing performance (resistant to lubrication layer loss), and the coating maintains high light transmittance, making it suitable for anti-icing of optical windows or windshields; Example 8, using a polydopamine biomimetic coating as a universal anchoring layer for grafting, maintains low adhesion (<50kPa) after repeated de-icing shearing, verifying the anti-icing capability of complex non-metallic composite material surfaces.

[0093] The above-mentioned appropriate surface anchoring strategies (such as phosphonic acid-based, siloxane-based, or polydopamine transition layers) for different substrate materials, combined with the selection of hygroscopic polymer monomers and the control of reaction conditions (affecting initiator assembly density and hydration layer thickness), can obtain high-performance anti-icing coatings at many material interfaces. While maintaining extremely low ice adhesion, they also have good anti-icing durability and good versatility.

[0094] It should be emphasized that the above are merely preferred embodiments of the present invention and are not intended to limit the present invention in any way. Any simple modifications, equivalent changes and alterations made to the above embodiments based on the technical essence of the present invention shall still fall within the scope of the technical solution of the present invention.

Claims

1. A method for preparing a polymer-modified surface with anti-icing properties, characterized in that: Includes the following steps: S1, the surface of the substrate material is activated by hydroxylation, and then immersed in an initiator monolayer assembly solution to complete surface self-assembly; the initiator monolayer has surface anchoring groups and initiating groups; S2, the substrate material that has completed surface self-assembly is immersed in a reaction system containing hygroscopic polymer monomers, catalysts and ligands to carry out a polymerization reaction, forming a hygroscopic polymer brush layer on the substrate material, and obtaining a polymer-modified surface with anti-icing performance. The substrate material is a metallic material, an inorganic non-metallic material, a polymer material, or a composite material thereof; The hygroscopic polymer monomer is at least one of oligoethylene glycol monomers, zwitterionic monomers, methacrylate monomers, and methacrylamide monomers.

2. The preparation method according to claim 1, characterized in that: The metal material is selected from one of titanium, titanium alloy, aluminum, aluminum alloy, iron, steel, stainless steel, copper alloy, and magnesium alloy; The inorganic non-metallic material is selected from one of glass, quartz, silicon wafers, and ceramics; The polymer material is selected from polyurethane and epoxy resin; The composite material is selected from glass fiber composite material and carbon fiber composite material.

3. The preparation method according to claim 1, characterized in that: The molar ratio of the hygroscopic polymer monomer, catalyst, and ligand is 100–2000:1:1–3; preferably, the molar ratio of the hygroscopic polymer monomer, catalyst, and ligand is 100–500:1:1–2.

4. The preparation method according to claim 3, characterized in that: The moisture-absorbing polymer monomer is at least one of oligoethylene glycol alkyl ether acrylate, polyethylene glycol methacrylate, sulfobetaine methacrylate, carboxybetaine methacrylate, 2-methacryloyloxyethyl phosphocholine, hydroxyethyl methacrylate, and N,N-dimethylacrylamide. The catalyst is cuprous bromide or cuprous chloride; The ligand is one of pentamethyldiethylenetriamine, 2,2'-bipyridine, or tris(2-dimethylaminoethyl)amine.

5. The preparation method according to claim 1, characterized in that: The hydroxylation activation treatment is at least one of oxygen plasma treatment, ultraviolet-ozone treatment, strong acid etching treatment, strong alkali etching treatment, and strong chemical oxidation treatment.

6. The preparation method according to claim 1, characterized in that: The initiator monolayer assembly solution comprises an initiator monomolecule and an inert diluent molecule, with a molar ratio of 1:9 to 9:

1. Preferably, the inert diluent molecule is a saturated straight-chain alkyl monophosphonic acid or a saturated branched alkyl monophosphonic acid; more preferably, it is at least one of C1-C20 saturated straight-chain alkylphosphonic acid, C4-C18 branched alkylphosphonic acid, and perfluorinated saturated alkylphosphonic acid. Preferably, the surface anchoring group of the initiator monomolecule is selected from one of phosphonic acid group, siloxane group, carboxyl group, and catechol group, and the initiating group of the initiator monomolecule is one of one of brominated alkyl terminal group, chloroalkyl terminal group, brominated ester terminal group, and chloroester terminal group.

7. The preparation method according to claim 1, characterized in that: The reaction system includes a solvent, which is at least one of tetrahydrofuran, water, methanol, ethanol, and N,N-dimethylformamide.

8. The preparation method according to claim 1, characterized in that: The polymerization reaction is carried out in a non-oxidizing atmosphere at a temperature of 20–90°C for a time of 1–48 h; preferably, the reaction temperature is 30–70°C for a time of 6–24 h.

9. A polymer-modified surface with anti-icing properties, prepared by any one of claims 1 to 8.

10. The application of the polymer-modified surface with anti-icing properties as described in claim 9 in an anti-icing environment.