CN117264493A - Ice-coating-preventing coating with photo-thermal effect and fan blade - Google Patents
Ice-coating-preventing coating with photo-thermal effect and fan blade Download PDFInfo
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- CN117264493A CN117264493A CN202311214488.3A CN202311214488A CN117264493A CN 117264493 A CN117264493 A CN 117264493A CN 202311214488 A CN202311214488 A CN 202311214488A CN 117264493 A CN117264493 A CN 117264493A
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- 239000011246 composite particle Substances 0.000 claims description 10
- 239000003607 modifier Substances 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 8
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical group [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 claims description 6
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 5
- 229940117986 sulfobetaine Drugs 0.000 claims description 5
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- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 claims description 4
- ZSZRUEAFVQITHH-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 2-(trimethylazaniumyl)ethyl phosphate Chemical compound CC(=C)C(=O)OCCOP([O-])(=O)OCC[N+](C)(C)C ZSZRUEAFVQITHH-UHFFFAOYSA-N 0.000 claims 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- 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
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/70—Wind energy
- Y02E10/72—Wind turbines with rotation axis in wind direction
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Abstract
The invention relates to the technical field of anti-icing, provides a low-ice adhesion anti-icing coating with a photo-thermal effect and a fan blade, and solves the problem that an anti-icing effect of a hydrophobic polymer coating in a low-temperature and high-humidity environment is poor due to the fact that the anti-icing performance of the photo-thermal deicing and the anti-icing performance of a hydrophobic lubricating coating are taken into consideration. The anti-icing coating with the photo-thermal effect comprises a surface layer formed by compounding a hydrogel component, a hydrophobic polymer component and photo-thermal micro-nano particles, wherein the hydrogel component and the hydrophobic polymer component form a double-network structure which is mutually inserted, the photo-thermal micro-nano particles comprise first photo-thermal particles and second photo-thermal particles with different particle diameters, and the first photo-thermal particles and the second photo-thermal particles are arranged in layers in the surface layer. The double-network structure of the hydrogel component and the hydrophobic polymer not only can endow the coating with better hydrophobic ice adhesion resistance. Meanwhile, the layered structure of the first photo-thermal particles and the second photo-thermal particles plays a positive role in anti-icing, and permeation of small molecular pollutants is prevented.
Description
Technical Field
The invention relates to the technical field of ice prevention, in particular to an ice coating preventing coating with a photo-thermal effect and a fan blade.
Background
The icing and frosting phenomenon brings great inconvenience to the production and life of people, and causes great economic loss, especially for some equipment needing to operate in cold environment, such as wind power generation blades and aircraft propellers, once ice layer adhesion exists on the surface of the equipment in operation, the dead weight of the equipment is greatly increased, the center of gravity is deviated during operation, surrounding flow fields are changed, the performance of the equipment is greatly influenced, and even serious consequences can be caused due to equipment damage.
In order to solve the problem of icing or frosting of the device, a number of surface heating structures and surface coating materials for the device have been proposed in the prior art. The electric heating deicing can continuously heat the deicing, but has the advantages of high energy consumption, high cost and complex construction process; although photo-thermal deicing can utilize renewable natural resources, it is limited by environmental weather and cannot provide a continuous and effective deicing effect; the surface coating material utilizes the hydrophobic and lubricating properties of the material to realize the effects of anti-icing, deicing, reducing the ice adhesion strength and anti-frosting on the surface of equipment, such as a fluorine-containing polymer coating, but the hydrophobic material has low adhesion with the surface of the equipment, has poor anti-seepage effect on small molecular pollutants in corrosive fluid, and greatly reduces the ice adhesion resistance of the hydrophobic polymer coating in a high-humidity cold environment.
Disclosure of Invention
The invention provides a low-ice adhesion anti-icing coating with a photo-thermal effect and a fan blade, which can give consideration to the anti-icing performance of photo-thermal deicing and a hydrophobic lubrication coating, and can solve the problem that the anti-icing effect of a hydrophobic polymer coating in a low-temperature and high-humidity environment is poor.
The low-ice-adhesion anti-icing coating with the photo-thermal effect comprises a surface layer formed by compounding a hydrogel component, a hydrophobic polymer component and photo-thermal micro-nano particles, wherein the hydrogel component and the hydrophobic polymer component form a double-network structure which is mutually inserted, the photo-thermal micro-nano particles comprise first photo-thermal particles and second photo-thermal particles with different particle diameters, and the first photo-thermal particles and the second photo-thermal particles are alternately layered and distributed in the surface layer.
According to the technical scheme, firstly, the photo-thermal micro-nano particles can absorb sunlight and convert the sunlight into heat, and the hydrogel component and the hydrophobic polymer cooperatively form an anti-adhesion lubricating layer on the surface of the coating, so that the coating has hydrophobic lubricating performance. Thereby enabling the coating to have both hydrophobic lubrication low ice adhesion performance and photo-thermal deicing performance.
Secondly, first photo-thermal particles and second photo-thermal particles with different particle sizes are distributed in a layered manner in the surface layer, and smaller particles can be relatively distributed at the gap positions of larger particles, so that large agglomeration of the particles is effectively reduced, photo-thermal micro-nano particles can be more uniformly dispersed in the coating, and sunlight capturing efficiency is high. Meanwhile, the layered arrangement with staggered size and particle diameter has better high specific surface area, and the layered reflection of different particle diameters can promote the absorption and capture of sunlight, so that the coating has better photo-thermal performance.
Finally, the double-network structure of the hydrogel component and the hydrophobic polymer not only can endow the coating with good hydrophobic ice adhesion resistance, but also can bind water molecules on the surface of the coating through hydrophilic sites in an environment with low temperature and high humidity to form confined water, reduce the freezing point of liquid and form a water lubricating layer, can reduce the surface roughness of the coating and reduce the contact area between ice and the coating, so that the ice adhesion strength is obviously reduced. Meanwhile, the layered structure of the first photo-thermal particles and the second photo-thermal particles can effectively generate a gas-resistance buffer layer, plays a positive role in delaying freezing of the surface of the coating under the supercooling condition, greatly reduces solid-liquid interfaces and prevents permeation of micromolecular pollutants in corrosive fluid.
As a preferred technical scheme, the photo-thermal micro-nano particles comprise nano silicon dioxide particles, and the hydrophobic polymer component is polydimethylsiloxane.
According to the preferable technical scheme, the nano silicon dioxide particles and the polydimethylsiloxane are connected through the silica bond to form a network structure with Si-O-Si bonds, and the network structure is inserted between hydrogel components, so that on one hand, the adhesion between the particles can be enhanced, on the other hand, super-hydrophobic micro-nano coarse structures can be formed on the surface and the inside of the coating, the hydrophobic ice adhesion resistance of the surface of the coating is further improved, the coating is endowed with high wear-resistant self-repairing performance, and even if the micro-nano coarse structures on the surface are worn, the exposed new surface still has a new micro-nano coarse structure.
As the preferable technical scheme, the photo-thermal micro-nano particles are composite particles of ferroferric oxide particles and nano silicon dioxide particles, and the nano silicon dioxide particles are coated on the surfaces of the ferroferric oxide particles.
According to the preferable technical scheme, the surface of the ferroferric oxide particles is coated with the silicon dioxide particles, so that the agglomeration of the ferroferric oxide particles can be further reduced, the photo-thermal micro-nano particles can be uniformly dispersed, the ferroferric oxide particles have excellent photo-thermal effect and can absorb sunlight and convert the sunlight into heat, the nano silicon dioxide can be attached to the surface of the ferroferric oxide particles, and an interpenetrating network is formed by the nano silicon dioxide and an external hydrophobic polymer, so that the structure of the coating is more stable. And a plurality of nano silicon dioxide is coated on the ferroferric oxide particles to form a rough surface of a concave-convex micro-nano structure, so that the coating has super-hydrophobic performance.
As a preferable technical scheme, the photo-thermal micro-nano particles further comprise a hydrophobic modifier, wherein the hydrophobic modifier is wrapped on the surfaces of the composite particles, and the hydrophobic modifier is fluorosilane.
According to the preferable technical scheme, the fluorosilane can improve the chemical hydrophobic performance of the photo-thermal micro-nano particles, namely, the hydrophobic anti-ice adhesion performance of the coating, and can reduce the surface energy of the photo-thermal micro-nano particles, thereby being beneficial to uniformly dispersing the photo-thermal micro-nano particles and promoting Si-O-Si bond connection between the surface of the photo-thermal micro-nano particles and the hydrophobic polymer.
As a preferable technical scheme, the particle size of the first photo-thermal particles is larger than that of the second photo-thermal particles, and the ratio of the particle size of the first photo-thermal particles to that of the second photo-thermal particles is 8-12.
According to the preferred technical scheme, experimental researches of the inventor find that the ratio of the particle sizes of the first photo-thermal particles to the second photo-thermal particles has better sunlight capturing efficiency between 8 and 12.
Further preferably, the particle size of the first photo-thermal particles is 200nm and the particle size of the second photo-thermal particles is 20nm.
According to the preferable technical scheme, when the particle size of the first photo-thermal particles is 200nm and the particle size of the second photo-thermal particles is 20nm, the second photo-thermal particles can just fill in gaps among the first photo-thermal particles, so that the anti-seepage performance of the coating can be improved, meanwhile, the capture efficiency of sunlight can be improved through layered reflection among the photo-thermal particles with different particle sizes, and the photo-thermal performance of the coating can be increased.
As a preferred technical scheme, the mass ratio of the first photo-thermal particles to the second photo-thermal particles is 1:2-2:1.
according to the preferred technical scheme, when the mass ratio of the first photo-thermal particles to the second photo-thermal particles is 1:2-2: when the range of 1 is within, the first photo-thermal particles and the second photo-thermal particles can be more uniformly and compactly layered in the coating, and the phenomenon of particle accumulation or agglomeration can not occur.
As a preferable technical scheme, the hydrogel component is a zwitterionic hydrogel obtained by crosslinking reaction of a zwitterionic monomer, a silane coupling agent and a free radical initiator, wherein the silane coupling agent has an olefin group.
According to the preferable technical scheme, the zwitterionic hydrogel can bind water molecules on the surface of the coating through hydrophilic sites to form limited water, and the freezing point of the surface of the coating is reduced, so that a water lubrication layer can be continuously formed on the contact interface of the coating and ice, and the lubrication ice-resistant adhesion performance of the surface of the coating is improved. And the silane coupling agent with olefin groups can also generate free radical polymerization with the zwitterionic monomer under the action of the free radical initiator to generate a polymer with a crosslinked network, and the structure is stable. In addition, strong chemical bonds are generated between the silane coupling agent and the polydimethylsiloxane and the nano silicon dioxide particles, so that the double-network structure between the hydrogel component and the hydrophobic polymer component is further promoted to be more stable.
As a preferable technical scheme, the zwitterionic monomer is one or more of dodecyl ethoxy sulfobetaine, carboxylic acid betaine methacrylate and 2-methacryloxyethyl phosphorylcholine, and the silane coupling agent is one or more of vinyl trimethoxy silane, allyl trimethoxy silane, triethoxy vinyl silane and allyl triethoxy silane.
Another aspect of the invention provides a fan blade provided with an anti-ice adhesion coating with photo-thermal effect as in any of the above-described aspects at its windward leading edge.
According to the technical scheme, as the windward front edge of the fan blade can form a windward surface during operation, the windward surface is often in direct contact with low-temperature humid air, icing and frosting can occur, and the anti-ice adhesion coating with the photo-thermal effect is arranged on the windward front edge of the fan blade, can inhibit the recrystallization of ice crystals on the windward surface of the fan blade, reduce the ice adhesion of the ice layers on the windward surface of the fan blade, and even if ice cubes are formed, the ice crystals cannot be blown off by air flow due to small ice crystal particles and cannot adhere on the windward surface, so that ice layer accumulation cannot be formed on the fan blade. When the fan runs in a low-temperature environment, the aerodynamic shape of the fan blade can be not influenced by the ice layer, and the aerodynamic performance can be kept.
Drawings
FIG. 1 is a line graph of ice cube slip angle versus temperature for sample coatings 1-5 prepared in an embodiment of the present invention;
fig. 2 is a line graph of the frosting delay time at different temperatures for sample coating 2 prepared in an embodiment of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In this embodiment, a low ice adhesion anti-icing coating having a photo-thermal effect is provided, which includes a surface layer formed by compounding a hydrogel component, a hydrophobic polymer component, and photo-thermal micro-nano particles.
The hydrogel component and the hydrophobic polymer component form a double-network structure which is mutually inserted, and the photo-thermal micro-nano particles comprise first photo-thermal particles and second photo-thermal particles with different particle diameters, wherein the first photo-thermal particles and the second photo-thermal particles are distributed in a staggered layered manner in the surface layer.
The hydrogel component and the hydrophobic polymer component can be interpenetrating network structures formed by a zwitterionic hydrogel and a hydrophobic polymer, specifically, the hydrogel component can be a zwitterionic hydrogel obtained by crosslinking one or more zwitterionic monomers of dodecyl ethoxy sulfobetaine, carboxylic acid betaine methacrylate and 2-methacryloxyethyl phosphorylcholine, the hydrophobic polymer is polydimethylsiloxane, and the crosslinking agent is silane coupling agent (one or more of vinyl trimethoxy silane, allyl trimethoxy silane, triethoxy vinyl silane and allyl triethoxy silane). The zwitterionic hydrogel can bind water molecules on the surface of the coating through hydrophilic points to form limited water, so that the freezing point of liquid on the surface of the coating is reduced, a water lubricating layer can be continuously formed on the contact interface between the coating and ice, the roughness of the surface of the coating is reduced, the contact area between ice cubes and the surface of the coating is reduced, and the lubricating and ice-resistant adhesive performance of the surface of the coating is improved. The polydimethylsiloxane has better strength, and can be crosslinked through strong chemical bonds and siloxane bonds, so that the hydrophobicity of the coating is improved.
It should be noted that, the coating in this embodiment adopts photo-thermal micro-nano particles as the filler, the photo-thermal micro-nano particles comprise nano silica particles, and the hydrophobic polymer component is polydimethylsiloxane. The nanometer silicon dioxide particles and the polydimethylsiloxane are connected through a silicon-oxygen bond to form a network structure with Si-O-Si bonds, and the network structure is inserted between hydrogel components, so that on one hand, the adhesion between particles can be enhanced, on the other hand, super-hydrophobic micro-nano coarse structures can be formed on the surface and the inside of the coating, the hydrophobic ice-resistant adhesion performance of the surface of the coating is further improved, the coating is endowed with high wear-resistant self-repairing performance, and even if the micro-nano coarse structures on the surface are worn, the exposed new surface still has a new micro-nano coarse structure.
Preferably, the photo-thermal micro-nano particles are composite particles of ferroferric oxide particles and nano silicon dioxide particles, and the nano silicon dioxide particles are coated on the surfaces of the ferroferric oxide particles. The surface of the ferroferric oxide particles is coated with the silicon dioxide particles, so that the agglomeration of the ferroferric oxide particles can be further reduced, the photo-thermal micro-nano particles can be uniformly dispersed, the ferroferric oxide particles have excellent photo-thermal effect and can absorb sunlight and convert the sunlight into heat, the nano silicon dioxide can be attached to the surface of the ferroferric oxide particles, and an interpenetrating network is formed by the nano silicon dioxide and an external hydrophobic polymer, so that the structure of the coating is more stable. And a plurality of nano silicon dioxide is coated on the ferroferric oxide particles to form a rough surface of a concave-convex micro-nano structure, so that the coating has super-hydrophobic performance.
Preferably, the photo-thermal micro-nano particles further comprise a hydrophobic modifier, wherein the hydrophobic modifier is wrapped on the surfaces of the composite particles, and the hydrophobic modifier is fluorosilane. The fluorosilane can improve the chemical hydrophobic property of the photo-thermal micro-nano particles, namely the hydrophobic ice-resistant adhesive property of the coating, and can reduce the surface energy of the photo-thermal micro-nano particles, thereby being beneficial to uniformly dispersing the photo-thermal micro-nano particles and promoting the Si-O-Si bond connection between the surface of the photo-thermal micro-nano particles and the hydrophobic polymer.
Wherein, preferably, the particle size of the first photo-thermal particles is larger than that of the second photo-thermal particles, and the ratio of the particle size of the first photo-thermal particles to that of the second photo-thermal particles is 8-12. The inventor experiment researches show that the ratio of the particle sizes of the first photo-thermal particles to the second photo-thermal particles has better sunlight capturing efficiency between 8 and 12. Further, the particle size of the first photo-thermal particles is 200nm, and the particle size of the second photo-thermal particles is 20nm. When the particle size of the first photo-thermal particles is 200nm and the particle size of the second photo-thermal particles is 20nm, the second photo-thermal particles can just fill in gaps among the first photo-thermal particles, so that the anti-seepage performance of the coating can be improved, meanwhile, the capture efficiency of sunlight can be improved through layered reflection among the photo-thermal particles with different particle sizes, and the photo-thermal performance of the coating can be increased.
Wherein, preferably, the mass ratio of the first photo-thermal particles to the second photo-thermal particles is 1:2-2:1. when the mass ratio of the first photo-thermal particles to the second photo-thermal particles is 1:2-2: when the range of 1 is within, the first photo-thermal particles and the second photo-thermal particles can be more uniformly and compactly layered in the coating, and the phenomenon of particle accumulation or agglomeration can not occur.
For example, the preparation method of the low ice adhesion anti-icing coating with photo-thermal effect in the present embodiment may be:
firstly, the surface of ferroferric oxide is attached by utilizing tetraethoxysilane to generate nano silicon dioxide particles to form composite particles. Then, fluorosilane is used as a hydrophobic modifier to be dripped into the solution of the composite particles, and after washing and drying, the photothermal micro-nano particles with two different particle diameters are obtained through grinding with different degrees.
Zwitterionic monomers (one or more of dodecyl ethoxy sulfobetaine, carboxylic acid betaine methacrylate and 2-methacryloxyethyl phosphorylcholine) and silane coupling agents (one or more of vinyl trimethoxy silane, allyl trimethoxy silane, triethoxy vinyl silane and allyl triethoxy silane) are reacted to obtain the zwitterionic hydrogel.
Finally, after mixing the zwitterionic hydrogel and the two photo-thermal micro-nano particles with different sizes, adding the prepolymer (methyl siloxane) of the hydrophobic polymer component and the curing agent, and curing to obtain the low-ice adhesion anti-icing coating with the photo-thermal effect in the embodiment.
In this embodiment, first, the photo-thermal micro-nano particles can absorb sunlight to convert into heat, and the hydrogel component forms an anti-adhesion lubricating layer on the surface of the coating in cooperation with the hydrophobic polymer, so that the coating has hydrophobic lubricating property. Thereby enabling the coating to have both hydrophobic lubrication low ice adhesion performance and photo-thermal deicing performance.
Secondly, first photo-thermal particles and second photo-thermal particles with different particle sizes are distributed in a layered manner in the surface layer, and smaller particles can be relatively distributed at the gap positions of larger particles, so that large agglomeration of the particles is effectively reduced, photo-thermal micro-nano particles can be more uniformly dispersed in the coating, and sunlight capturing efficiency is high. Meanwhile, the layered arrangement with staggered size and particle diameter has higher specific surface area, and the layered reflection of different particle diameters can promote the absorption and capture of sunlight, so that the coating has better photo-thermal performance.
Finally, the double-network structure of the hydrogel component and the hydrophobic polymer not only can endow the coating with good hydrophobic ice adhesion resistance, but also can bind water molecules on the surface of the coating through hydrophilic sites in an environment with low temperature and high humidity to form confined water, reduce the freezing point of liquid and form a water lubricating layer, can reduce the surface roughness of the coating and reduce the contact area between ice and the coating, so that the ice adhesion strength is obviously reduced. Meanwhile, the layered structure of the first photo-thermal particles and the second photo-thermal particles can effectively generate a gas-resistance buffer layer, plays a positive role in delaying freezing of the surface of the coating under the supercooling condition, greatly reduces solid-liquid interfaces and prevents penetration of corrosive fluid and pollutants.
The performance of the low ice adhesion anti-icing coating with photo-thermal effect provided by this embodiment is further demonstrated in the experiments below.
1. Material preparation
1.1 preparation of photo-thermal micro-nanoparticles
To 100ml of the absolute ethanol solution were added 4ml of ammonium hydroxide and 20ml of distilled water, and the ferroferric oxide nanoparticles were added to the mixed solution and stirred at room temperature for 1h. Subsequently, ethyl orthosilicate (2 ml) was slowly poured into the above mixed solution drop by drop, stirring was continued for 1 hour, and nano silica particles were formed by attaching to the surface of the ferroferric oxide to form composite particles. Then, fluorodecyl (tripropoxy) silane (1 mL) was added dropwise as a hydrophobic modifier to the above-described mixed solution of uniform composite particles, and magnetically stirred at 40℃for 12 hours. Finally, drying and grinding to obtain the photo-thermal micro-nano particles, purifying by using a magnet, and washing for a plurality of times by using deionized water.
By controlling the grinding time in the same way, 160nm and 20nm photothermal micro-nano particles, 200nm and 20nm photothermal micro-nano particles and 240nm and 20nm photothermal micro-nano particles are respectively prepared.
1.2 preparation of hydrogel Components
The method comprises the steps of adding a zwitterionic monomer (dodecyl ethoxy sulfobetaine), a silane coupling agent (vinyl trimethoxy silane) and a free radical initiator into a solvent of ethanol and water according to a proportion, wherein the reaction environment is nitrogen atmosphere, the reaction temperature is 70 ℃, and the zwitterionic hydrogel is obtained after mechanical stirring and the reaction time is 1h.
1.3 preparation of Low Ice adhesion anti-icing coating with photothermal Effect
The zwitterionic hydrogel was dissolved in aqueous ethanol according to 2:1 (the mass ratio of the first photo-thermal particles to the second photo-thermal particles is 1:1), dispersing the polydimethylsiloxane prepolymer and the curing agent into the mixed solution according to the mass ratio of 1:0.1, coating the mixed solution on the surface of a substrate, curing for 2 hours at 80 ℃, forming a double-network interpenetrating structure by Polydimethylsiloxane (PDMS) and zwitterionic hydrogel, forming an interpenetrating network structure with Si-O-Si bonds with the nano particles, and simultaneously adsorbing the second photo-thermal particles around the first photo-thermal particles under the action of the silicon-oxygen bonds, wherein when the first photo-thermal particles are sequentially arranged, the upper layer and the lower layer are respectively provided with a second photo-thermal particle layer which is arranged in a manner of being embedded between the first photo-thermal particles, so that the first photo-thermal particles and the second photo-thermal particles are alternately arranged, and preparing sample coating 1 (160 nm and 20nm, mass ratio 1:1), sample coating 2 (200 nm and 20nm, mass ratio 1), sample coating 2 (3:20 nm and mass ratio 1) and sample coating 1:240 nm are prepared
In addition, based on photo-thermal micro-nano particles with two sizes of 200nm and 20nm, the mass ratio of the photo-thermal micro-nano particles is 2:1 and 1:2 respectively, so that a sample coating 4 (200 nm and 20nm, mass ratio of 2:1) and a sample coating 5 (200 nm and 20nm, mass ratio of 1:2) are obtained.
2. Characterization of materials
2.1 hydrophobic and anti-Ice adhesion Properties of sample coating
The sample coating was subjected to a water droplet adhesion experiment, and the morphology and adhesion of the water droplets on the surface of the sample coating were recorded by video observation.
In the water drop adhesion test, the hydrostatic contact angle and the rolling angle of the sample coatings 1-5 are about 150 degrees and 5 degrees, wherein the hydrostatic contact angle of the sample coating 3 and the sample coating 5 is larger than 155 degrees, the hydrophobicity is better, and particularly the hydrostatic contact angle of the sample coating 3 reaches 159 degrees, because the mass ratio of the first photo-thermal particles and the second photo-thermal particles with the sizes of 240nm and 20nm is 1:1, a more uniform micro-nano rough surface can be formed, and the micro-nano rough surface has better superhydrophobicity.
Then, the water drops contacting the surface of the sample coating are removed by the needle, and the water drops are easily taken away by the needle and do not adhere to the surface of the coating, which shows that the sample coating prepared by the embodiment has better hydrophobic property and ice adhesion resistance, and can prevent the adhesion of the water drops on the surface and ice crystals, thereby achieving the effect of inhibiting the nucleation of ice crystals.
Sample coatings 1-5 and uncoated substrates were placed in a temperature controlled vessel and then cooled to-10 ℃, -20 ℃, -30 ℃, -40 ℃ respectively. Specifically, a liftable platform is arranged in the temperature control container for placing a substrate, liquid nitrogen is arranged below the platform for cooling, and the temperature is controlled by adjusting the distance between the lifting platform and the liquid nitrogen device. After the lifting platform is adjusted to a proper height, when the substrate on the platform is consistent with the ambient temperature, ice cubes (10 mm) with the same size are placed on the substrate and kept for 10min, then the lifting platform is controlled to slowly incline to one side, and the inclination angle of the platform when the ice cubes slide is recorded as a sliding angle.
FIG. 1 is a line graph showing the ice slip angle versus temperature for sample coatings 1-5. Since the uncoated substrate was already unable to slip at-20 ℃, no data were entered for the uncoated substrate in fig. 1.
As shown in fig. 1, the sliding angle of the sample coatings 1-5 is substantially unchanged at temperatures above-20 ℃, and the lowest sliding angle of the sample coatings is also smaller than that of the uncoated substrate (about 5 °), because the zwitterionic hydrogels can bind water molecules on the surfaces of the coatings to form confined water, lower the liquid freezing point of the surfaces of the sample coatings, form a water lubricating layer, can cooperate with hydrophobic PDMS to reduce ice adhesion, and therefore ice cubes more easily slide off the surfaces of the sample coatings 1-5.
When the ambient temperature is below-20 ℃, the slip angle of sample coatings 1 and 4 starts to increase, and the slip angle of the other sample coatings remains unchanged until the slip angle of all sample coatings increases, but ice cubes remain unattached to the sample coating surface, when the ambient temperature is below-40 ℃. It can be concluded that the sample coating prepared in this embodiment is still capable of maintaining excellent anti-ice adhesion properties at low temperatures.
2.2 solar light absorption Properties of sample coating
The solar absorptivity test is carried out on the sample coating 1-5, the solar absorptivity of the sample coating 2 obtained by the test is highest and reaches 97.7%, and other sample coatings also have excellent solar absorptivity, wherein the solar absorptivity of the sample coating 1 is 89.1%; the solar absorptivity of sample coating 3 was 93.4%; the solar absorptivity of sample coating 4 was 95.7%; the solar absorptivity of sample coating 5 was 94.5%.
The first photo-thermal particles and the second photo-thermal particles with different particle sizes are layered in the surface layer, and smaller particles can be relatively distributed at the gap positions of larger particles, so that large agglomeration of the particles is effectively reduced, the photo-thermal micro-nano particles can be more uniformly dispersed in the coating, and the sunlight capturing efficiency is high. Meanwhile, the layered arrangement with staggered size particle diameters has higher specific surface area, layered reflection of different particle diameters can promote sunlight absorption and capture, for example, 20nm second photo-thermal particles can be embedded into arrangement gaps among 200nm first photo-thermal particles, sunlight is captured by upper first photo-thermal particles, part of sunlight penetrates through gaps of the first photo-thermal particles to be downwards captured by lower denser second photo-thermal particles, part of sunlight reflected on the surfaces of the first photo-thermal particles can be captured by upper second photo-thermal particles, and multiple diffuse reflection can be generated on the surfaces of two layers of photo-thermal particles with different particle diameters, so that the coating has better sunlight absorptivity.
2.3 anti-frost Properties of sample coating
Sample coating 2 was placed in a temperature controlled container. The temperature of the temperature-controlled vessel was controlled to-10 ℃, -20 ℃, -30 ℃ and-40 ℃, then a gentle water spray was generated in the temperature-controlled vessel using an air humidifier (99% relative humidity, 0.04L/h water consumption) and the time delay of frosting was recorded when the substrate surface became opaque or frosted.
FIG. 2 is a line graph showing the frosting delay time of a sample coating at different temperatures. As shown in fig. 2, it can be seen that the sample coating prepared in this embodiment can maintain a higher frosting delay time even in a low-temperature and high-humidity environment, because the sample coating has a hydrophilic hydrogel, and can bind water molecules on the surface of the coating through hydrophilic sites to form confined water, so as to reduce the freezing point of liquid, and can still form a water lubrication layer under the low-temperature and high-humidity conditions, so that the sample coating has a better ice adhesion resistance.
Particularly, the layered arrangement of the first photo-thermal particles and the second photo-thermal particles in the embodiment can greatly reduce the infiltration of small molecular water vapor, reduce solid-liquid interfaces, and is favorable for delaying the frosting of the surface of the coating under the supercooling condition, so that the coating has better anti-icing and anti-frosting effects compared with the common double-network hydrogel coating.
In other embodiments of the present invention, there is also provided a fan blade having a wind-facing leading edge provided with an anti-ice adhesion coating having a photo-thermal effect as in any of the above-described aspects. Because the windward front edge of the fan blade can form a windward surface when in operation, the windward surface is often in direct contact with low-temperature moist air, icing and frosting can occur, and the anti-ice adhesion coating with a photo-thermal effect is arranged on the windward front edge of the fan blade, can inhibit the recrystallization of ice crystals on the windward surface of the fan blade, reduce the ice adhesion of the ice layer on the windward surface of the fan blade, and can be blown down by air flow due to small ice crystal particles even if ice cakes are formed, and can not form ice layer accumulation on the fan blade. When the fan runs in a low-temperature environment, the aerodynamic shape of the fan blade can be not influenced by the ice layer, and the aerodynamic performance can be kept.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (10)
1. The anti-icing coating with the photo-thermal effect is characterized by comprising a surface layer formed by compounding a hydrogel component, a hydrophobic polymer component and photo-thermal micro-nano particles, wherein the hydrogel component and the hydrophobic polymer component form a double-network structure which is mutually penetrated, the photo-thermal micro-nano particles comprise first photo-thermal particles and second photo-thermal particles with different particle diameters, and the first photo-thermal particles and the second photo-thermal particles are alternately layered in the surface layer.
2. The anti-icing coating having a photothermal effect according to claim 1, wherein said photothermal micro-nanoparticles comprise nanosilica particles and said hydrophobic polymer component is polydimethylsiloxane.
3. The anti-icing coating with photo-thermal effect as claimed in claim 2, wherein the photo-thermal micro-nano particles are composite particles of ferroferric oxide particles and nano silicon dioxide particles, and the nano silicon dioxide particles are coated on the surfaces of the ferroferric oxide particles.
4. The anti-icing coating with photo-thermal effect as recited in claim 3, wherein the photo-thermal micro-nano particles further comprise a hydrophobic modifier wrapped on the surface of the composite particles, and the hydrophobic modifier is fluorosilane.
5. An anti-icing coating having a photothermal effect according to any of claims 1-4, wherein the particle size of said first photothermal particles is larger than the particle size of said second photothermal particles, and the ratio of the particle size of said first photothermal particles to the particle size of said second photothermal particles is from 8 to 12.
6. The anti-icing coating having a photothermal effect according to claim 4, wherein the first photothermal particle has a particle size of 200nm and the second photothermal particle has a particle size of 20nm.
7. The anti-icing coating with photo-thermal effect of claim 6 wherein the mass ratio of the first photo-thermal particles to the second photo-thermal particles is 1:2-2:1.
8. the anti-icing coating with photothermal effect according to claim 1, wherein the hydrogel component is a zwitterionic hydrogel obtained by reacting a zwitterionic monomer, a silane coupling agent and a free radical initiator, the silane coupling agent having an olefinic group.
9. An anti-icing coating having a photothermal effect as claimed in claim 8, wherein said zwitterionic monomer is one or a combination of more of dodecyl ethoxy sulfobetaine, carboxylic acid betaine methacrylate, 2-methacryloyloxyethyl phosphorylcholine,
the silane coupling agent is one or a combination of more of vinyl trimethoxy silane, allyl trimethoxy silane, triethoxy vinyl silane and allyl triethoxy silane.
10. A fan blade, characterized in that the windward leading edge of the fan blade is provided with an anti-icing coating with a photo-thermal effect as claimed in any of claims 1-9.
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