CN117447971A - Preparation method of n-tetradecane phase-change microcapsule powder and anti-icing coating - Google Patents
Preparation method of n-tetradecane phase-change microcapsule powder and anti-icing coating Download PDFInfo
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- CN117447971A CN117447971A CN202311786794.4A CN202311786794A CN117447971A CN 117447971 A CN117447971 A CN 117447971A CN 202311786794 A CN202311786794 A CN 202311786794A CN 117447971 A CN117447971 A CN 117447971A
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- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 title claims abstract description 224
- 239000003094 microcapsule Substances 0.000 title claims abstract description 118
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 238000000576 coating method Methods 0.000 title claims abstract description 76
- 239000011248 coating agent Substances 0.000 title claims abstract description 60
- 239000000843 powder Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000004814 polyurethane Substances 0.000 claims abstract description 48
- 229920002635 polyurethane Polymers 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 238000002844 melting Methods 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 10
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 9
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- XZUAPPXGIFNDRA-UHFFFAOYSA-N ethane-1,2-diamine;hydrate Chemical compound O.NCCN XZUAPPXGIFNDRA-UHFFFAOYSA-N 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000003973 paint Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 230000001804 emulsifying effect Effects 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000008859 change Effects 0.000 abstract description 30
- 238000012695 Interfacial polymerization Methods 0.000 abstract description 5
- 230000008014 freezing Effects 0.000 abstract description 5
- 238000007710 freezing Methods 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000011527 polyurethane coating Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 13
- 238000002425 crystallisation Methods 0.000 description 10
- 230000008025 crystallization Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 230000004580 weight loss Effects 0.000 description 9
- 238000004146 energy storage Methods 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 238000002411 thermogravimetry Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 239000012782 phase change material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005338 heat storage Methods 0.000 description 4
- 230000006399 behavior Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
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- 239000003595 mist Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
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- 238000001757 thermogravimetry curve Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- UJCHIZDEQZMODR-BYPYZUCNSA-N (2r)-2-acetamido-3-sulfanylpropanamide Chemical compound CC(=O)N[C@@H](CS)C(N)=O UJCHIZDEQZMODR-BYPYZUCNSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001669680 Dormitator maculatus Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 230000033228 biological regulation Effects 0.000 description 1
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- 238000004364 calculation method Methods 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 238000001816 cooling Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
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- 230000000630 rising effect Effects 0.000 description 1
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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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
- C09D7/63—Additives non-macromolecular organic
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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
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
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Abstract
The invention discloses n-tetradecane phase-change microcapsule powder and a preparation method of an anti-icing coating, and belongs to the technical field of anti-icing coatings. The invention achieves the purpose of delaying the rapid temperature reduction and provides a method for preventing ice and freezing rain. The invention takes n-tetradecane as a raw material, adopts an interfacial polymerization method to prepare n-tetradecane phase-change microcapsule, and is mixed with a polyurethane coating to form the n-tetradecane phase-change microcapsule polyurethane anti-icing coating. The invention has great application potential in the aspects of phase change microcapsule phase change latent heat and delaying the icing of wind turbine blades.
Description
Technical Field
The invention belongs to the technical field of anti-icing coatings, and particularly relates to a preparation method of n-tetradecane phase-change microcapsule powder and a preparation method of n-tetradecane phase-change microcapsule polyurethane anti-icing coatings.
Background
With the exhaustion of fossil energy resources, the demand for renewable energy is increasing. Wind energy has become a popular choice worldwide due to its wide distribution, great potential for development and environmental friendliness.
In recent years, global climate change is aggravated, and the icing phenomenon of the wind turbine is a natural phenomenon which frequently occurs in winter and spring alternating seasons. The icing problem caused by severe extreme weather such as extremely cold and freezing rain frequently appears to bring serious influence to wind power generation equipment, especially in northeast region wind turbine blade icing phenomenon often appears, when the blade icing amount exceeds a limit, only can stop processing to prevent to produce huge influence to the electric wire netting, this can not only cause huge economic loss, also easily causes the damage of electric wire netting accident and the property such as vehicle, nearby building or other local structures of stopping simultaneously and personnel casualties in the deicing process.
Wind turbine blade deicing may be divided into two main categories, passive and active. Active type typically includes solution deicing, mechanical deicing, balloon deicing. Passive types are typically electrothermal material coatings, photothermal material coatings, and superhydrophobic material coatings. However, various technologies exist today to prevent ice from forming with short plates, and there is still no economical and efficient method for preventing ice from forming on blades. Therefore, research on wind turbine generator blade ice prevention and removal theory still needs to be solved.
Phase change materials refer to substances that change physical properties with temperature changes and can provide latent heat. The phase change material has been used for improving the freezing resistance of cold area buildings, n-tetradecane is used as the phase change material in Honda et al, expanded graphite is used as a carrier, and the C14/EG composite phase change material prepared by a porous adsorption method can change phase before water is frozen, so that the freezing resistance of cement-based materials is improved.
Disclosure of Invention
Icing is a common physical phenomenon, and icing caused by frequent occurrence of extreme weather can bring serious influence to wind power generation equipment, wherein the icing influence of wind turbine blades is most prominent, and research on ice prevention and removal mechanisms and methods of the wind turbine blades is a scientific front-end difficult problem to be solved urgently.
The phase-change microcapsule prepared by the invention is a good energy storage material, the phase-change material, namely n-tetradecane phase-change microcapsule powder, is encapsulated in a shell material, so that the leakage problem of the phase-change material is solved, and energy can be effectively stored.
In order to realize the technical problems, the invention adopts the following technical scheme:
the invention aims to provide a preparation method of n-tetradecane phase-change microcapsule powder, which is realized by the following steps:
dropwise adding a catalyst into n-tetradecane, and simultaneously dropwise adding isophorone diisocyanate (IPDI) dropwise until a transparent solution is obtained, sealing after the dropwise adding is finished, and melting to obtain an oil phase;
adding deionized water into Sodium Dodecyl Sulfate (SDS), and emulsifying to obtain a water phase;
adding the oil phase into the water phase, homogenizing at 60 ℃, transferring the mixture into a reactor while the mixture is hot, dropwise adding half of ethylenediamine water solution at 80 ℃ while stirring, reacting for 3 hours, continuously dropwise adding the rest ethylenediamine water solution dropwise, reacting for 6 hours, filtering, and drying to obtain n-tetradecane phase-change microcapsule powder;
wherein the catalyst is a mixture of petroleum ether and dibutyl tin dilaurate.
Further defined, 1 drop of catalyst was added dropwise to 3 grams of n-tetradecane, with an isophorone diisocyanate (IPDI) dosage of 2 grams; the mass ratio of petroleum ether to dibutyl tin dilaurate is 9.9:0.1.
Further defined, 50 grams deionized water was added to 0.05 grams Sodium Dodecyl Sulfate (SDS).
Further defined, the aqueous ethylenediamine solution is prepared by adding 1.275 grams of ethylenediamine to 24.43 grams of water.
Further defined, the dripping of the ethylenediamine aqueous solution is slowly performed drop by drop with a rubber head dropper.
Further defined, during the dropwise addition, mechanical stirring was carried out at a rate of 2000 rpm.
Further defined, the rotational speed of the homogenization is 10000rpm and the homogenization time is 3min.
N-tetradecane phase-change microcapsule powder prepared by any method.
The invention further provides a preparation method of the n-tetradecane phase-change microcapsule polyurethane anti-icing coating, which comprises the steps of grinding the n-tetradecane phase-change microcapsule powder prepared by any method, mixing the ground n-tetradecane phase-change microcapsule powder with polyurethane paint, coating the mixture on the surface of a substrate, and curing the mixture to obtain the n-tetradecane phase-change microcapsule polyurethane anti-icing coating.
Further defined, curing is performed at 100 ℃ for 1 hour.
Compared with the prior art, the invention has the following beneficial effects:
the invention takes n-tetradecane as a raw material, adopts an interfacial polymerization method to prepare the n-tetradecane phase-change microcapsule, and is mixed with a polyurethane anti-icing coating to form the n-tetradecane phase-change microcapsule polyurethane anti-icing coating, and the n-tetradecane phase-change microcapsule polyurethane anti-icing coating is applied to a wind turbine blade, has the melting enthalpy and the crystallization enthalpy of 90.814J/g and 96.273J/g respectively, has the same coating rate and energy storage efficiency, shows that the n-tetradecane phase-change microcapsule has better heat energy storage capacity, and carries out a 5-min icing wind tunnel test, the icing quality of the n-tetradecane phase-change microcapsule polyurethane anti-icing coating is reduced by 30.53 percent at most, and the icing area is reduced by 26.34 percent at most, thus the coating has good anti-icing effect. The invention provides a method for preventing ice and freezing rain for the purpose of delaying the rapid temperature reduction of the phase change microcapsule phase change latent heat. Has great application potential in the aspect of phase change latent heat of phase change microcapsules and delaying the icing of wind turbine blades.
The microcapsule is applied to the anti-icing coating of the blade, is applied to the blade of the wind turbine, can delay the rapid reduction of the temperature, improves the performance and the operation efficiency of wind power equipment, can prevent or even prevent the damage of icing to the fields of high-voltage transmission, rail traffic and the like, has important significance to the development of important industries such as electric power, traffic and the like, and has good application prospect.
For a further understanding of the nature and the technical aspects of the present invention, reference should be made to the following detailed description of the invention and the accompanying drawings, which are provided for reference and illustration only and are not intended to limit the invention.
Drawings
FIG. 1 is a NACA0018 blank vane;
FIG. 2 shows a surface of a blade with n-tetradecane phase-change microcapsule polyurethane anti-icing coating;
FIG. 3 is a photograph of an icing wind tunnel system and test site of NACA 0018;
FIG. 4 is a photograph of n-tetradecane phase-change microcapsules;
FIG. 5 is a 500-fold magnification of an n-14 alkane phase change microcapsule;
FIG. 6 is a 1000-fold magnification of an n-14 alkane phase change microcapsule;
FIG. 7 is a 500-fold magnification of the coating surface;
FIG. 8 is a coating cross section at 500 times magnification;
FIG. 9 is a DSC graph of n-tetradecane, n-tetradecane phase change microcapsules, n-tetradecane phase change microcapsule polyurethane anti-icing coatings;
FIG. 10 is a TGA graph of n-tetradecane phase change microcapsules versus n-tetradecane phase change microcapsule polyurethane anti-icing coating;
FIG. 11 is a DTG plot of n-tetradecane phase change microcapsules versus an n-tetradecane phase change microcapsule polyurethane anti-icing coating;
FIG. 12 is a graph showing the icing shape of two coatings at-5℃at different wind speeds;
FIG. 13 is a graph showing the icing shape of two coatings at-10℃at different wind speeds;
FIG. 14 is a graph showing the icing shape of two coatings at-15℃at different wind speeds;
FIG. 15 is a graph of icing quality for two coatings at different wind speeds and different temperatures;
FIG. 16 is a graph of the area of two coatings at different wind speeds and different temperatures.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will facilitate a further understanding of the present patent by those skilled in the art and are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present patent.
Example 1: in this example, n-tetradecane was used as a material, and chemical reagents, inc., national medicine group. N-tetradecane with melting point of 6 ℃ and density of 0.762g/cm 3 The liquid state was maintained at room temperature. Isophorone diisocyanate (IPDI), shanghai microphone Biochemical technologies Co., ltd; sodium Dodecyl Sulfate (SDS), national drug group chemical company limited; dibutyl tin dilaurate, shanghai microphone Biochemical technology Co., ltd; petroleum ether, tianjin chemical agent Co., ltd; ethylenediamine, national pharmaceutical chemicals limited. NACA0018 blade airfoil, chord length 100mm. The test anti-icing performance should be operated in icing wind tunnels. Deionized water was used throughout the experiment unless otherwise specified.
In this embodiment, the preparation of the n-tetradecane phase-change microcapsule powder is performed according to the following steps:
firstly, preparing an oil phase material:
early preparation: 9.9 g of petroleum ether and 0.1 g of dibutyl tin dilaurate were homogeneously mixed as a catalyst.
Preparing an oil phase: firstly, weighing 3 g of n-tetradecane, placing the n-tetradecane into a beaker, dropwise adding a drop of catalyst and 2g of isophorone diisocyanate (IPDI) into the beaker, sealing the mixture through a preservative film, placing the mixture into a heat-collecting type constant-temperature heating magnetic stirrer, and melting the mixture for 30min at 60 ℃, thus obtaining an oil phase with a core-shell ratio of 6:4.
The second is the preparation of water phase material: 0.05 g of Sodium Dodecyl Sulfate (SDS) was placed in a beaker, 50 g of deionized water was poured into the beaker, and the mixture was emulsified in a homogenizer at 60℃and 10000rpm for 3 minutes to obtain a water phase.
N-tetradecane phase-change microcapsules were subsequently prepared:
early preparation: adding 1.275 g of ethylenediamine into 24.43 g of water, uniformly mixing to prepare an ethylenediamine aqueous solution
Preparation of phase-change microcapsules: firstly, adding an oil phase into a water phase, mixing, homogenizing for 3min in a homogenizer at 60 ℃ and 10000rpm, and transferring the homogenized oil phase into a three-necked flask at 60 ℃; stirring at the temperature of 80 ℃ at the rate of 2000rmp, dropwise adding half of ethylenediamine water solution while stirring, continuously dropwise adding the rest ethylenediamine water solution after reacting for 3 hours, after the reaction is completed for 6 hours, performing suction filtration by a suction filtration device, and drying at room temperature for 24 hours; obtaining the n-tetradecane phase-change microcapsule powder.
Ethylenediamine is added as a cross-linking agent in the first three hours, the reaction is intense, and the flask is milky.
The preparation method of the n-tetradecane phase-change microcapsule polyurethane anti-icing coating in the embodiment comprises the steps of grinding the n-tetradecane phase-change microcapsule powder prepared in the embodiment 1, mixing with polyurethane paint, coating the mixture on the surface of an airfoil of a NACA0018 blade, hanging the coated blade on the top of a beaker, putting the beaker into an oven, and curing for 1 hour at 100 ℃ to obtain the n-tetradecane phase-change microcapsule polyurethane anti-icing coating.
The effect of the present invention was verified by the following experiment.
In the embodiment, n-tetradecane is used as a core material, isophorone diisocyanate (IPDI for short) is used as a shell material, and the n-tetradecane phase-change microcapsule polyurethane anti-icing coating is prepared by an interfacial polymerization method. The microstructure and morphology were characterized using a Scanning Electron Microscope (SEM). The heat storage characteristics of the phase-change microcapsules are measured by a Differential Scanning Calorimeter (DSC) and the coating rate and the energy storage efficiency of the n-tetradecane phase-change microcapsules are calculated. The thermal stability of the phase-change microcapsules was analyzed by thermogravimetric analysis (TGA). The n-tetradecane phase change microcapsule polyurethane anti-icing coating is formed by mixing with the polyurethane anti-icing coating and is coated on the NACA0018 wind turbine blade (as in FIG. 1). And finally, carrying out dynamic icing experiments under different wind speeds and temperatures by adopting an icing wind tunnel system (shown in figure 2), comparing the icing quality and icing area of the blade coated with the polyurethane anti-icing coating and the blade coated with the n-tetradecane phase-change microcapsule polyurethane anti-icing coating, and calculating the anti-icing rate of the n-tetradecane phase-change microcapsule polyurethane anti-icing coating.
The invention adopts an SEM electron microscope to analyze the morphology of the n-tetradecane phase-change microcapsule and the polyurethane anti-icing coating of the n-tetradecane phase-change microcapsule. And analyzing the phase change temperature and the phase change enthalpy of the n-tetradecane phase change microcapsule at the temperature of between 50 ℃ below zero and 70 ℃ and the speed of 10 ℃/min by adopting a DSC differential scanning calorimeter, analyzing the thermal storage characteristic of the n-tetradecane phase change microcapsule, and calculating the coating rate and the energy storage efficiency of the phase change microcapsule. And adopting a TGA thermogravimetric analyzer to carry out thermogravimetric analysis on the n-tetradecane phase-change microcapsule and the n-tetradecane phase-change microcapsule polyurethane anti-icing coating at the temperature of 30-600 ℃ and the speed of 10 ℃/min under the nitrogen range.
1. Anti-icing test
Dynamic icing experiments are carried out by using an icing wind tunnel system, and fig. 3 is photographs of the icing wind tunnel system and a test site of NACA0018, wherein the temperatures of the icing wind tunnel system are set to-5 ℃, -10 ℃, -15 ℃. The wind speed was set to 3m/s, 6m/s, 9m/s. The supercooled air sucked by the wind tunnel is combined with the water mist, and the low-temperature water mist is sprayed onto the surface of the blade model by the water sprayer. The wind tunnel test section is rectangular with dimensions of 250 mm ×200 mm. And measuring the icing mass of the blade through a balance, drawing the icing shape of the blade through CAXA CAD, observing the icing shape and measuring the icing area.
The phase-change microcapsule prepared by the interfacial polymerization method has high encapsulation rate, good mechanical resistance and simple preparation process. Therefore, we select interfacial polymerization method to prepare n-tetradecane phase-change microcapsule, and the prepared microcapsule is shown in figure 4.
2. SEM test
And analyzing the morphology and microstructure of the n-tetradecane phase-change microcapsule and the n-tetradecane phase-change microcapsule polyurethane anti-icing coating by using a scanning electron microscope. Fig. 5 and 6 show the surface micro-morphology of the n-tetradecane phase-change microcapsule, and as can be seen from fig. 5 and 6, the surface of the n-tetradecane phase-change microcapsule forms a small sphere, and the size is uniform and the morphology is regular, because the stable oil-in-water emulsion prepared in the earlier stage is coated in the shell material after 6 hours of reaction, and the phase-change latent heat occurs after the phase-change temperature is reached. Fig. 7 is a schematic diagram of fig. 8 showing the surface and cross section of a coating layer of n-tetradecane phase-change microcapsules attached to polyurethane, wherein small irregular holes appear on the surface of the coating layer, and the pore structure of the surface of the coating layer enhances the attachment of the phase-change microcapsules. The heat storage performance of the polyurethane anti-icing coating is enhanced due to the adhesion of the phase-change microcapsules. Fig. 8 shows that n-tetradecane phase-change microcapsules are distributed in the pores of the polyurethane anti-icing coating. SEM test results prove that the prepared phase-change microcapsule has an obvious core-shell structure and accords with the structure of the microcapsule.
3. DSC test and calculation of coating Rate and coating efficiency
Since the energy storage efficiency and the coating rate are key factors and preconditions for evaluating the phase-change microcapsule material, DSC test is performed on the prepared phase-change microcapsule, and the phase-change performance of the prepared phase-change microcapsule is evaluated.
DSC curves (see FIG. 9) of the n-tetradecane, the n-tetradecane phase-change microcapsules and the n-tetradecane polyurethane anti-icing coating are observed, and the n-tetradecane phase-change microcapsules are found to have bimodal exothermic behaviors in the cooling process and quasi-unimodal endothermic behaviors in the melting process. Pure n-tetradecane tm=7.07 ℃, the melting enthalpy shown in the endothermic process can reach 172.88J/g, tc=0.79 ℃, and the crystallization enthalpy shown in the exothermic process is 182.2J/g. The small difference between the melting enthalpy and the crystallization enthalpy indicates its stable thermal energy storage capacity.
Tm=7.44 ℃, the melting enthalpy of the n-tetradecane phase-change microcapsule is 90.814J/g in the endothermic process, tc= -16.94 ℃, the heat release is sustained in the range of-30 ℃ to 5 ℃, and the crystallization enthalpy in the exothermic process is 96.273J/g. Compared with pure n-tetradecane, the Tm of the microcapsule is advanced, which indicates the high thermal conductivity of the phase-change microcapsule. N-tetradecane polyurethane paint tm=5.93 ℃, exhibits a crystallization enthalpy of 13.495J/g during heat release, and a crystallization enthalpy of 13.74J/g during heat release at tc= -17.35 ℃. Furthermore, as can be seen from the DSC profile, the melting and crystallization temperature ranges of n-tetradecane phase-change microcapsules and n-tetradecane phase-change microcapsule polyurethane anti-icing coatings are also greater than that of n-tetradecane.
The coating ratio R of the microcapsules was calculated from the melting enthalpy obtained from DSC scan according to the following formula:
1 (1)
Wherein ΔHm, micro-PCM and ΔHm, PCM are the melting enthalpies of the phase change microcapsules and n-tetradecane, respectively.
Based on the enthalpy of phase change, the energy storage efficiency (E) is generally used as an index of the microcapsule for the storage and release of latent heat, and can be obtained by the following formula:
2, 2
Wherein ΔHc, micro-PCM and ΔHc, PCM is the crystallization enthalpy of phase-change microcapsule and n-tetradecane, respectively.
The phase change behavior and heat storage characteristics of n-tetradecane phase change microcapsules were studied by using n-tetradecane as a control, and DSC curves and corresponding phase change data are shown in table 1.
TABLE 1
Tm: a melting temperature; Δhm: enthalpy of fusion; tc: crystallization temperature; Δhc: enthalpy of crystallization
The obtained microcapsule has 53% of coating rate and 53% of coating efficiency, has excellent latent heat storage capacity in the phase change process, and can meet the application of the microcapsule in the aspect of heat regulation.
4. TGA test
To determine the thermal stability of the as-synthesized thermal capsules, we need to perform TGA testing of the samples. The method is mainly characterized by the weight loss temperature and weight loss percentage of the sample, wherein the temperature range of the thermal weight is 30-600 ℃, and the temperature rising rate is 10 ℃ per minute under the nitrogen range. TGA curves of n-tetradecane phase-change microcapsules and n-tetradecane phase-change microcapsule polyurethane anti-icing coatings and DTG curves after data processing are measured, and are shown in the following figures: figures 10 and 11 show the TGA curve and DTG curve of n-tetradecane phase-change microcapsule and n-tetradecane phase-change microcapsule polyurethane anti-icing coating, and it can be obtained from the figures that three obvious mass loss processes occur in the temperature range of 30-600 ℃, the first stage is that the weight loss temperature range is 150-200 ℃, mainly because the moisture adsorbed on the surface of the n-tetradecane phase-change microcapsule volatilizes when encountering heat, the sample is not completely dried, and contains part of water, so that larger weight loss occurs in the temperature range of 150-200 ℃, but the determination of the TGA of the sample is not affected. The weight loss temperature range of the second stage is 200-250 ℃, and the quality of the n-tetradecane phase-change microcapsule is rapidly reduced along with the temperature rise, mainly the core material n-tetradecane volatilizes when being heated, and the integral structure of the phase-change microcapsule is destroyed to cause quality loss; the third stage has a weight loss temperature in the range of 300-350 deg.c, mainly due to the decomposition of the wall material. The n-tetradecane phase-change microcapsule polyurethane anti-icing coating has two weight loss processes, the weight loss temperature ranges from 250 ℃ to 300 ℃ in two stages, the weight loss temperature interval is larger than that of the n-tetradecane phase-change microcapsule, and the quality loss of the n-tetradecane phase-change microcapsule and the n-tetradecane phase-change microcapsule polyurethane anti-icing coating is stable after the temperature is 400 ℃. Therefore, the n-tetradecane phase-change microcapsule polyurethane anti-icing coating has good thermal stability in the temperature range of 30-250 ℃, and can be coated on a wind turbine blade to delay the icing of the wind turbine blade.
5. Wind tunnel dynamic icing test
In order to explore the anti-icing effect of the n-tetradecane phase-change microcapsule polyurethane anti-icing coating, the coating and the blank polyurethane anti-icing coating are respectively coated on an NACA0018 blade airfoil, an icing wind tunnel experiment is repeated three times, the quality of the coating on the blade is controlled to be the same, three groups of parallel experiments are performed, icing wind tunnel experiments are performed at the temperature of-5 ℃, the temperature of-10 ℃ and the temperature of-15 ℃ at the wind speed of 3m/s, the wind speed of 6m/s and the wind speed of 9m/s, and after 5min of icing wind tunnel experiments, icing occurs on the front edge of the blade. And weighing the frozen blade airfoil by using a balance after 5min, recording ice by using a high-definition camera, observing the frozen shape, and comparing the anti-icing effects of the two coating models by using poor frozen quality and frozen area. As the temperature decreases and the wind speed increases, more and more water droplets collide with the blade surface, forming thicker ice.
Fig. 12, 13, 14 are ice-on diagrams of two coatings at different wind speeds and different temperatures. It is obvious that the icing area of the polyurethane anti-icing coating of the n-tetradecane phase-change microcapsule is far smaller than that of the polyurethane anti-icing coating at the same temperature and the same wind speed. Fig. 15 and 16 are bar graphs of icing quality and icing area for two coatings, and the calculated anti-icing rate of the n-tetradecane phase change microcapsule polyurethane anti-icing coating is up to 30.53%, and the icing area is reduced by up to 26.34%. At the same wind speed, the lower the temperature, the slightly reduced the anti-icing rate. However, the ice weight and the ice area of the n-tetradecane phase-change microcapsule polyurethane anti-icing coating are still far smaller than those of the polyurethane anti-icing coating, which proves that the n-tetradecane phase-change microcapsule polyurethane anti-icing coating has good anti-icing effect.
Claims (10)
1. The preparation method of the n-tetradecane phase-change microcapsule powder is characterized by comprising the following steps of: dropwise adding a catalyst into n-tetradecane, dropwise adding IPDI (IPDI) until a transparent solution is obtained, sealing after the dropwise adding is finished, and melting to obtain an oil phase; adding deionized water into sodium dodecyl sulfate, and emulsifying to obtain a water phase; adding the oil phase into the water phase, homogenizing at 60 ℃, transferring the mixture into a reactor while the mixture is hot, dropwise adding half of ethylenediamine water solution at 80 ℃ while stirring, reacting for 3 hours, continuously dropwise adding the rest ethylenediamine water solution dropwise, reacting for 6 hours, filtering, and drying to obtain n-tetradecane phase-change microcapsule powder; wherein the catalyst is a mixture of petroleum ether and dibutyl tin dilaurate; to 3 g of n-tetradecane, 1 drop of catalyst was added dropwise, and the amount of IPDI was 2 g.
2. The method for preparing n-tetradecane phase-change microcapsule powder according to claim 1, wherein the mass ratio of petroleum ether to dibutyl tin dilaurate is 9.9:0.1.
3. The method of preparing n-tetradecane phase-change microcapsule powder according to claim 2, wherein 50 g deionized water is added to 0.05 g sodium dodecyl sulfate.
4. A process for preparing n-tetradecane phase-change microcapsule powder according to claim 3, characterized in that ethylenediamine solution is added to 24.43 g water by 1.275 g ethylenediamine.
5. The method for preparing n-tetradecane phase-change microcapsule powder according to claim 1, wherein the melting is performed at 60 ℃.
6. The method for preparing n-tetradecane phase-change microcapsule powder according to claim 1, wherein the n-tetradecane phase-change microcapsule powder is added dropwise while stirring at a rate of 2000 rpm.
7. The method for preparing n-tetradecane phase-change microcapsule powder according to claim 1, wherein the homogenizing is carried out for 3min at a rotation speed of 10000 rpm.
8. An n-tetradecane phase-change microcapsule powder prepared by the method of preparing an n-tetradecane phase-change microcapsule powder according to any of claims 1-7.
9. The preparation method of the n-tetradecane phase-change microcapsule polyurethane anti-icing coating is characterized in that the n-tetradecane phase-change microcapsule powder prepared by the method of any one of claims 1-7 is ground and then mixed with polyurethane paint, coated on the surface of a substrate, and cured to obtain the n-tetradecane phase-change microcapsule polyurethane anti-icing coating.
10. The method for preparing an n-tetradecane phase-change microcapsule polyurethane anti-icing coating according to claim 9, wherein the curing is performed at 100 ℃ for 1 hour.
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