CN116948522A - Anti-icing coating and preparation method and application thereof - Google Patents

Anti-icing coating and preparation method and application thereof Download PDF

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Publication number
CN116948522A
CN116948522A CN202310988701.XA CN202310988701A CN116948522A CN 116948522 A CN116948522 A CN 116948522A CN 202310988701 A CN202310988701 A CN 202310988701A CN 116948522 A CN116948522 A CN 116948522A
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China
Prior art keywords
rigid high
icing
strength
coating
strength resin
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CN202310988701.XA
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Chinese (zh)
Inventor
陈华伟
刘晓林
王泽林澜
赵泽辉
陈憬唐
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Beihang University
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Beihang University
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Priority to CN202310988701.XA priority Critical patent/CN116948522A/en
Publication of CN116948522A publication Critical patent/CN116948522A/en
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D183/00Coating 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
    • C09D183/04Polysiloxanes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/70Wind energy
    • Y02E10/72Wind turbines with rotation axis in wind direction

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention provides an anti-icing coating, a preparation method and application thereof, and belongs to the technical field of ice prevention and removal. The method comprises the steps of mixing a rigid high-strength resin precursor with an organic silicon resin precursor to obtain a mixed solution; mixing the mixed solution, a rigid high-strength resin curing agent, a silicone resin curing agent and a catalyst to obtain a dispersion; and coating the dispersion liquid on the surface of the substrate, and then carrying out crosslinking and curing to obtain the anti-icing coating. According to the invention, the rigid high-strength resin precursor is cured to form the rigid high-strength resin, the organic silicon resin precursor is cured to form the organic silicon resin, the rigid high-strength resin and the organic silicon resin are crosslinked, the rigid high-strength resin and the organic silicon resin form an interpenetrating polymer network, and the prepared anti-icing coating can adjust the elastic modulus of the surface, has better strength, can maintain the anti-icing performance of an interface for a long time, and meets the anti-icing requirement of the wind turbine blade.

Description

Anti-icing coating and preparation method and application thereof
Technical Field
The invention relates to the technical field of ice prevention and removal, in particular to an anti-icing coating and a preparation method and application thereof.
Background
Ice control technology has attracted attention in many fields. Because the wind turbine generator is exposed to the natural environment for a long time, the wind turbine generator is greatly affected by the environment and the climate, wherein the icing of the blades is the most important factor affecting the safety and the power generation of the wind turbine generator. The blade icing can lead to the change of blade airfoil, influences the unit output, can lead to the unit to shut down and produce great power curve deviation when serious, causes the generated energy loss to can influence the balance of impeller, lead to the uneven load of blade and drive part, influence the life and the operation safety of unit. In addition, the detachment of ice coating due to the rotation of the blower may jeopardize the safety of surrounding population and property. Therefore, it is very urgent and necessary to prevent ice from being removed for the wind power generator.
Compared with the traditional anti-icing mode, namely hot air/electric heating anti-icing, the anti-icing coating has extremely excellent anti-icing effect, does not need energy consumption, is energy-saving and environment-friendly, and is focused by researchers. Coating anti-icing is free of energy and system constraints and is considered to be one of the most important components of new generation anti-icing systems.
Superhydrophobic surfaces and lubricant injection surfaces are the most typical passive anti-icing surfaces, which rely on lotus leaf-inspired solid-air interfaces and nepenthes-inspired solid/liquid interfaces, respectively. Poor durability makes it difficult for these surfaces to remain functional for long periods of time in harsh external environments, particularly under high speed, high pressure or high shear conditions. The soft elastic surface is used as a newly developed anti-icing strategy, can promote the generation of interfacial fracture, leads to ice separation, realizes low ice adhesion strength, and can be used for large-area anti-icing and deicing. Its use in harsh environments is limited by the deterioration of mechanical robustness caused by the ultra-low modulus of elasticity. It remains a challenge for interfacial cracking to promote an ice-shedding interface that achieves ultra-low ice adhesion and maintains a strong mechanical robustness.
Disclosure of Invention
In view of the above, the present invention aims to provide an anti-icing coating, and a preparation method and application thereof. The anti-icing coating prepared by the invention can adjust the elastic modulus of the surface, has better strength, can maintain the anti-icing performance of the interface for a long time, and meets the anti-icing requirement of the wind power generation blade.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of an anti-icing coating, which comprises the following steps:
mixing a rigid high-strength resin precursor with an organic silicon resin precursor to obtain a mixed solution;
mixing the mixed solution, a rigid high-strength resin curing agent, a silicone resin curing agent and a catalyst to obtain a dispersion;
and coating the dispersion liquid on the surface of the substrate, and then carrying out crosslinking and curing to obtain the anti-icing coating.
Preferably, the rigid high strength resin precursor includes one or more of polyurethane, epoxy, fluorosilicone, acrylic, and polyurea resins.
Preferably, the mass fraction of the rigid high-strength resin precursor in the mixed solution is 0-100%, and the mass fraction of the rigid high-strength resin precursor is not 100% nor 0.
Preferably, the silicone resin precursor includes one or more of hydroxyl silicone oil, amino silicone oil, divinyl terminated silicone oil, and polydimethylsiloxane.
Preferably, the rigid high strength resin curative comprises one or more of polyetheramine, polyamide, amine hexafluorophosphate and isocyanate.
Preferably, the mass of the rigid high-strength resin curing agent is 5% -50% of the mass of the rigid high-strength resin precursor.
Preferably, the silicone resin curing agent comprises one or more of ethyl orthosilicate, tetrabutyl silicate, tetrabutyl titanate, and ethyl titanate.
Preferably, the mass of the organic silicon resin curing agent is 5-30% of the mass of the organic silicon resin precursor.
The invention also provides an anti-icing coating prepared by the preparation method of the technical scheme, which comprises an interpenetrating polymer network formed by the rigid high-strength resin and the organic silicon resin.
The invention also provides application of the anti-icing coating in the anti-icing field for wind power generation.
The invention provides a preparation method of an anti-icing coating, which comprises the following steps: mixing a rigid high-strength resin precursor with an organic silicon resin precursor to obtain a mixed solution; mixing the mixed solution, a rigid high-strength resin curing agent, a silicone resin curing agent and a catalyst to obtain a dispersion; and coating the dispersion liquid on the surface of the substrate, and then carrying out crosslinking and curing to obtain the anti-icing coating.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the rigid high-strength resin precursor is cured to form the rigid high-strength resin, the organic silicon resin precursor is cured to form the organic silicon resin, the rigid high-strength resin and the organic silicon resin are crosslinked, the rigid high-strength resin and the organic silicon resin form an interpenetrating polymer network, and the prepared anti-icing coating can adjust the elastic modulus of the surface, has better strength, can maintain the anti-icing performance of an interface for a long time, and meets the anti-icing requirement of the wind turbine blade.
The preparation method is simple and convenient, can prepare in a large area, can design anti-icing surfaces with different elastic moduli according to requirements, and has excellent strength and strong adhesion with a substrate; simple raw materials, low preparation cost, economy and environmental protection (no solvent is added).
The data of the examples show that the anti-icing coating prepared by the invention has extremely high mechanical strength, extremely high liquid repellency and extremely high anti-icing performance.
Drawings
FIG. 1 is a physical view of anti-icing coatings for wind power generation prepared in examples and comparative examples;
FIG. 2 is a schematic view showing the structure of the anti-icing coating for wind power generation prepared in examples and comparative examples;
FIG. 3 is ice adhesion force data of anti-icing coatings for wind power generation prepared in examples and comparative examples;
FIG. 4 shows ice accumulation conditions in dynamic environments of the anti-icing coating blades for wind power generation prepared in the examples and the comparative examples;
FIG. 5 shows ice accumulation conditions of the wind power generation anti-icing coating blades prepared in the examples and the comparative examples in a dynamic environment;
fig. 6 shows anti-icing conditions of the anti-icing coated blades for wind power generation prepared in examples and comparative examples, wherein (1) is example 1, (2) is example 2, and (3) is comparative example 1.
Detailed Description
The invention provides a preparation method of an anti-icing coating, which comprises the following steps:
mixing a rigid high-strength resin precursor with an organic silicon resin precursor to obtain a mixed solution;
mixing the mixed solution, a rigid high-strength resin curing agent, a silicone resin curing agent and a catalyst to obtain a dispersion;
and coating the dispersion liquid on the surface of the substrate, and then carrying out crosslinking and curing to obtain the anti-icing coating.
In the present invention, all materials used are commercial products in the art unless otherwise specified.
The invention mixes the rigid high-strength resin precursor and the organic silicon resin precursor to obtain the mixed solution.
In the present invention, the rigid high-strength resin precursor preferably includes one or more of polyurethane, epoxy resin, fluorosilicone resin, acrylic resin, and polyurea resin.
In the present invention, the mass fraction of the rigid high-strength resin precursor in the mixed solution is preferably 0 to 100%, and the mass fraction of the rigid high-strength resin precursor is not 100% nor 0, more preferably 25 to 50%.
In the present invention, the silicone resin precursor preferably includes one or more of hydroxyl silicone oil, amino silicone oil, divinyl end-capped silicone oil, and polydimethylsiloxane.
In the present invention, the mixing preferably includes the following steps in order: and fully mixing the rigid high-strength resin precursor and the organic silicon resin precursor, mechanically stirring, and ultrasonically dispersing and defoaming until the solution is clear. The specific parameters of the thorough mixing, mechanical stirring and ultrasonic dispersion and deaeration are not particularly limited, and the method is well known to those skilled in the art.
After the mixed solution is obtained, the mixed solution, the rigid high-strength resin curing agent, the organic silicon resin curing agent and the catalyst are mixed to obtain the dispersion liquid.
In the present invention, the catalyst is preferably added after the rigid high-strength resin and the silicone resin curing agent are added to the mixed solution.
In the present invention, the rigid high-strength resin curing agent preferably includes one or more of polyetheramine, polyamide, amine hexafluorophosphate and isocyanate. In the present invention, the type of the rigid high-strength resin curing agent preferably corresponds to the rigid high-strength resin precursor, and the rigid high-strength resin precursor undergoes different chemical reactions, and the corresponding may be performed in a manner well known to those skilled in the art, specifically, as follows: when the rigid high-strength resin precursor is polyurethane, polyol groups of the polyurethane react with isocyanate curing agents, and when the rigid high-strength resin precursor is epoxy resin, ring-opening reaction of epoxy groups of the epoxy resin occurs, wherein the curing agents are polyether amine, polyamide or fatty amine.
In the present invention, the mass of the rigid high-strength resin curing agent is preferably 5% to 50% of the mass of the rigid high-strength resin precursor.
In the present invention, the silicone resin curing agent preferably includes one or more of ethyl orthosilicate, tetrabutyl silicate, tetrabutyl titanate, and ethyl titanate.
In the invention, the mass of the organic silicon resin curing agent is preferably 5-30% of the mass of the organic silicon resin precursor.
In the present invention, the catalyst preferably includes one or more of dibutyltin dilaurate, stannous octoate, and dibutyltin diacetate.
In the present invention, the mass percentage of the rigid high-strength resin precursor in the dispersion is preferably 0% to 94.81%, the mass percentage of the rigid high-strength resin curing agent is preferably 0% to 49.9%, the mass percentage of the silicone resin precursor is preferably 0% to 94.81%, the mass percentage of the silicone resin curing agent is preferably 0% to 29.94%, and the mass percentage of the catalyst is preferably 0.2% to 1%.
After the dispersion liquid is obtained, the anti-icing coating is obtained by coating the surface of the substrate with the dispersion liquid and then carrying out crosslinking and curing.
In the present invention, the substrate is preferably made of glass fiber board, metal, cloth, glass or equipment requiring anti-icing.
In the present invention, the substrate is preferably subjected to washing and then coated with the dispersion, and the washing agent for washing preferably includes ethanol, acetone, xylene or water.
In the present invention, the coating is preferably a brush coating or a roll coating, and the specific parameters of the brush coating or the roll coating are not particularly limited, and may be any means known to those skilled in the art.
In the invention, the crosslinking curing is preferably carried out at room temperature for 12 hours or at 80 ℃ for 2 hours.
After the completion of the crosslinking and curing, the present invention is preferably further dried, and the specific manner of drying is not particularly limited in the present invention, and may be any manner known to those skilled in the art.
The invention also provides an anti-icing coating prepared by the preparation method of the technical scheme, which comprises an interpenetrating polymer network formed by the rigid high-strength resin and the organic silicon resin.
The invention also provides application of the anti-icing coating in the anti-icing field for wind power generation.
The anti-icing coating provided by the present invention, and the method of making and using it, are described in detail below in conjunction with the examples for further illustration of the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
(1) Fully mixing E51 type epoxy resin and hydroxyl silicone oil, and mechanically stirring, ultrasonically dispersing and defoaming to obtain a first dispersion liquid;
(2) Adding polyether amine and tetraethoxysilane into the dispersion liquid I, and fully stirring to obtain a dispersion liquid II;
(3) Adding dibutyl tin dilaurate into the dispersion liquid II, and stirring to obtain a dispersion liquid III;
(4) Cleaning the wind blade and the glass substrate with a cleaning agent, and drying;
(5) Uniformly coating the dispersion liquid III on the surface of the substrate by adopting a brushing process;
(6) And standing the brushed sample for 12 hours at room temperature until the coating is fully crosslinked and cured and is completely dried and cured, so that the high-strength anti-icing coating for wind power generation is obtained.
The mass percent of the E51 type epoxy resin in the dispersion liquid III is 37.1 percent, the mass percent of the polyether amine is 12.4 percent, the mass percent of the dibutyl tin dilaurate is 1 percent, the mass percent of the hydroxyl silicone oil is 45 percent, and the mass percent of the tetraethoxysilane is 4.5 percent.
The coating had a white appearance (see fig. 1), had a low ice adhesion strength of 50.8kPa (see fig. 2), an elastic modulus of 432.8MPa (see fig. 3), an adhesive strength with the substrate of 5.73MPa (see fig. 4), and a thickness reduction of 60 μm after 250 cycles of grinding with a grinding wheel loaded with 250g (see fig. 5). It can effectively reduce the ice accumulation on the surface of the blade in dynamic environment (see figure 6).
Example 2
The same as in example 1, except that the mass percentage of the E51 type epoxy resin in the dispersion liquid III was 18.6%, the mass percentage of the polyether amine was 6.2%, the mass percentage of the dibutyltin dilaurate was 1%, the mass percentage of the hydroxy silicone oil was 67.4%, and the mass percentage of the tetraethoxysilane was 6.8%.
The coating had a white appearance (see fig. 1), had a low ice adhesion strength of 47kPa (see fig. 2), an elastic modulus of 1.1MPa (see fig. 3), an adhesive strength with the substrate of 4.21MPa (see fig. 4), and a thickness reduction of 90 μm (see fig. 5) after 250 cycles of grinding with a grinding wheel loaded with 250 g. It can effectively reduce the ice accumulation on the surface of the blade in dynamic environment (see figure 6).
Comparative example 1
(1) Mechanically stirring E51 type epoxy resin, and performing ultrasonic dispersion and defoaming to obtain a first dispersion liquid;
(2) Adding polyether amine into the dispersion liquid I and fully stirring to obtain a dispersion liquid II;
(3) Adding dibutyl tin dilaurate into the dispersion liquid II, and stirring to obtain a dispersion liquid III;
(4) Cleaning the wind blade and the glass substrate with a cleaning agent, and drying;
(5) Uniformly coating the dispersion liquid III on the surface of the substrate by adopting a brushing process;
(6) And standing the brushed sample for 12 hours at room temperature until the coating is fully crosslinked and cured and is completely dried and cured, so that the high-strength anti-icing coating for wind power generation is obtained.
Wherein the mass percent of the E51 type epoxy resin in the dispersion liquid III is 74.2 percent, the mass percent of the polyether amine is 24.8 percent, and the mass percent of the dibutyl tin dilaurate is 1 percent.
The coating had a transparent appearance (see FIG. 1), a relatively high ice adhesion strength of 316.4kPa (see FIG. 2), an elastic modulus of 1775.9MPa (see FIG. 3), an adhesive strength with the substrate of 6.37MPa (see FIG. 4), and a thickness reduction of 23 μm after 250 cycles of grinding with a 250g load of grinding wheel (see FIG. 5). But it is severe in dynamic environments with blade surface ice (see fig. 6).
Comparative example 2
(1) Mechanically stirring and ultrasonically dispersing and defoaming the hydroxy dimethyl silicone oil to obtain a first dispersion liquid;
(2) Adding tetraethoxysilane into the dispersion liquid I, and fully stirring to obtain a dispersion liquid II;
(3) Adding dibutyl tin dilaurate into the dispersion liquid II, and stirring to obtain a dispersion liquid III;
(4) Cleaning the wind blade and the glass substrate with a cleaning agent, and drying;
(5) Uniformly coating the dispersion liquid III on the surface of the substrate by adopting a brushing process;
(6) And standing the brushed sample for 12 hours at room temperature until the coating is fully crosslinked and cured and is completely dried and cured, so that the high-strength anti-icing coating for wind power generation is obtained.
Wherein the mass percentage of the hydroxy dimethyl silicone oil in the dispersion liquid III is 90 percent, the mass percentage of the tetraethoxysilane is 9 percent, and the mass percentage of the dibutyl tin dilaurate is 1 percent.
The coating had a clear appearance (see fig. 1), had a low ice adhesion strength of 45.6kPa (see fig. 2), an elastic modulus of 0.6MPa (see fig. 3), an adhesive strength with the substrate of 2.01MPa (see fig. 4), a poor strength, no abrasion resistance after abrasion, and a thickness reduction of 130 μm after 75 cycles of abrasion with a 250g load of grinding wheel (see fig. 5).
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be comprehended within the scope of the present invention.

Claims (10)

1. A method for preparing an anti-icing coating, comprising the steps of:
mixing a rigid high-strength resin precursor with an organic silicon resin precursor to obtain a mixed solution;
mixing the mixed solution, a rigid high-strength resin curing agent, a silicone resin curing agent and a catalyst to obtain a dispersion;
and coating the dispersion liquid on the surface of the substrate, and then carrying out crosslinking and curing to obtain the anti-icing coating.
2. The method of manufacturing according to claim 1, wherein the rigid high strength resin precursor comprises one or more of polyurethane, epoxy, fluorosilicone, acrylic, and polyurea resins.
3. The production method according to claim 1 or 2, wherein the mass fraction of the rigid high-strength resin precursor in the mixed liquid is 0 to 100%, and the mass fraction of the rigid high-strength resin precursor is not 100% nor 0.
4. The method of preparation of claim 1, wherein the silicone resin precursor comprises one or more of a hydroxyl silicone oil, an amino silicone oil, a divinyl terminated silicone oil, and a polydimethylsiloxane.
5. The method of claim 1, wherein the rigid high strength resin curative comprises one or more of polyetheramine, polyamide, amine hexafluorophosphate, and isocyanate.
6. The method of claim 1 or 5, wherein the mass of the rigid high-strength resin curing agent is 5% to 50% of the mass of the rigid high-strength resin precursor.
7. The method of claim 1, wherein the silicone resin curing agent comprises one or more of ethyl orthosilicate, tetrabutyl silicate, tetrabutyl titanate, and ethyl titanate.
8. The preparation method according to claim 1 or 7, wherein the mass of the silicone resin curing agent is 5-30% of the mass of the silicone resin precursor.
9. An anti-icing coating as claimed in any of claims 1 to 8 comprising an interpenetrating polymer network of a rigid high strength resin and a silicone resin.
10. Use of the anti-icing coating according to claim 9 in the anti-icing field for wind power generation.
CN202310988701.XA 2023-08-08 2023-08-08 Anti-icing coating and preparation method and application thereof Pending CN116948522A (en)

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Application Number Priority Date Filing Date Title
CN202310988701.XA CN116948522A (en) 2023-08-08 2023-08-08 Anti-icing coating and preparation method and application thereof

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Application Number Priority Date Filing Date Title
CN202310988701.XA CN116948522A (en) 2023-08-08 2023-08-08 Anti-icing coating and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN116948522A true CN116948522A (en) 2023-10-27

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