CN116554783A - Super-hydrophobic electrothermal anti-icing/deicing coating material and preparation method thereof - Google Patents
Super-hydrophobic electrothermal anti-icing/deicing coating material and preparation method thereof Download PDFInfo
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- CN116554783A CN116554783A CN202310438202.3A CN202310438202A CN116554783A CN 116554783 A CN116554783 A CN 116554783A CN 202310438202 A CN202310438202 A CN 202310438202A CN 116554783 A CN116554783 A CN 116554783A
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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
- 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
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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
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- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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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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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2003/085—Copper
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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Abstract
The utility model relates to a super-hydrophobic electrothermal anti-icing/deicing coating material and a preparation method thereof. The raw materials comprise the following components in parts by weight: 50-100 parts of low-surface-energy high-molecular material, 10-30 parts of carbon fiber and 5-40 parts of nano material. The preparation method comprises the following steps: and (3) weighing a certain amount of carbon fiber and conductive nano material, dispersing, adding a low-surface-energy polymer material, uniformly mixing at a high speed, and curing the coating to obtain the superhydrophobic electrothermal anti-icing/deicing coating. Compared with the prior art, the layer material has an active deicing function after being covered by the ice layer, and has high anti-icing/deicing reliability; the energy consumption required by electrothermal ice protection/removal is lower; the single material and single-layer coating structure are adopted, so that the heat conduction loss is low, the utilization rate is high, the anti-icing/deicing rate is high, the reliability of the coating is higher, and the service life of the coating is longer.
Description
Technical Field
The utility model belongs to the field of polymer composite materials, and particularly relates to a superhydrophobic electrothermal anti-icing/deicing coating material and a preparation method thereof.
Background
Anti-icing/deicing is a common major problem in the fields of aviation, wind power, power transmission and distribution and the like. For an aircraft, flying under icing meteorological conditions, parts such as wings and portholes of the aircraft can be quickly frozen and ice deposited, so that the stress condition and the flying attitude of the aircraft are changed, the energy consumption and the energy efficiency of the flight are influenced, and serious potential safety hazards (GaoT, luoZ, zhou Y, et al A level de-icing strategy combining electric-heating with plasma synthetic jet actuator, J Aerospace Engineering,2021 and Vol.235 (4) 513-522) are brought. In the wind field in the alpine region, the fan blades are easy to freeze and accumulate ice, after the blades are covered with ice, larger ice load can be generated, the original wing shape of the blades is changed, the load and the output of the wind turbine generator set are affected, the anti-icing/deicing energy consumption is additionally increased, the wind power generation efficiency is greatly reduced, the service life of the blades can be shortened, and potential safety hazards [ Zhang L, zhang H, liu Z, et al Nano-silicon anti-icing coatings for protecting wind-power turbine fan blades, journal of Colloid and Interface Science,2023,Volume 630,Part A,Pages1-10 ] are caused to the equipment and field personnel. In the field of power transmission and distribution, ice coating of a power transmission line is one of the most serious disasters of a power system, and accidents such as ice flash, overload, line galloping, even disconnection, tower inversion and the like of an insulator are caused by ice coating, so that the safe operation of a power grid is seriously threatened, and serious social and economic losses [ Laform J.L., allaire M.A., laflammeJ.State-of-the-art on power line de-icing, atmospheric Research,1998,Volume 46,Issues1-2 and pages 143-158 ] are brought to the country.
Aiming at the requirements of the fields of aircrafts, wind power, power transmission and distribution and the like, various anti-icing/deicing technologies have been developed. The anti-icing/deicing technology in the aeronautical field mainly comprises electrothermal deicing, mechanical deicing, hot gas deicing, chemical agent deicing and the like [ Gao T, luo Z, zhou Y, et al, A, level de-icing strategy combining electric-heating with plasma synthetic jet actuator, J Aerospace Engineering,2021, vol.235 (4) 513-522 ]. The mechanical deicing has the defects of low efficiency, energy consumption and high maintenance cost, and the structural damage to the surface of the aircraft can be caused in the deicing process; chemical agent deicing can only be applied to aircraft ground icing generally, and has certain harm to the environment; the trend of hot gas deicing along with the composite materials of aircraft components has also been increasingly limited in its development [ Zhao Z, chen H, zhu Y, et al a robust superhydrophobic anti-icing/de-icing composite coating with electrothermal and auxiliary photothermal performances, composites Science and Technology, volume 227,18August 2022,109578 ]. The electrothermal anti-icing/deicing has the advantages of easy control, high reliability, good position universality and the like because the heat is generated by utilizing a conductive network in the material, is compatible with the development trend of airplane composite material and pure electric chemical, and becomes one of the main anti-icing/deicing technologies of an airplane [ Redondo O, prolongo S.G., campo M, et al, anti-icing and de-icing coatings based Joule's heating of graphene nanoplatelets, composites Science and Technology, volume 164,18August2018,Pages 65-73 ]. Patent CN206602671U proposes a three-layer structure electric heating unit with insulating material layers vertically wrapped with metal electric heating films, which prevents the surface of the equipment from freezing or removes the surface ice by means of electric heating, has fast electric heating response speed and high temperature, shows excellent electric heating performance and anti-icing/deicing effect, is safe and reliable [ Bai, etc., chinese patent CN206602671U ]. Similar to an airplane, the wind power blade also often uses an electrothermal deicing technology, an electrothermal element is arranged at a position where the blade is easy to freeze, the thermal conductivity coefficient of the blade material is smaller, the thickness is thicker, and the electrothermal deicing effect by adopting the electrothermal element is good and the reliability is high. Patent CN105856586B relates to a graphene electrothermal film wind turbine blade icing protection system, adopts a graphene epoxy glass fiber laminated board structure, adopts different heating powers in different areas of the wind turbine blade, and effectively improves the working performance of the deicing system [ Li Hui and the like, chinese patent CN105856586B ].
In order to ensure flight safety, the electrothermal ice-proof function on the aircraft is often required to be started for a long time; although the electrothermal deicing function is on for a short time, high power output is required to ensure a quick and reliable deicing process. The influence on the power output, yaw of the wind turbine and power control can be up to 50% when the wind turbine blades are started for electrothermal deicing, and in order to achieve the purpose of deicing, the fan can generate power with excessive rated power, and the maximum power can be 16% higher than the rated power [ part O, ilica A.anti-icing and de-icing techniques for wind turbines: critical review, cold Regions Science and Technology, volume 65,Issue 1,January 2011,Pages 88-96 ].
The anti-icing surface with the surface micro/nano configuration is an anti-icing technology with zero energy consumption, the material surface is provided with super-hydrophobicity by constructing a surface micro/nano layered structure, the static water contact angle is more than 150 degrees, the anti-icing is prevented in a mode of repelling water drop adhesion, and the problems of icing and ice accumulation are solved without energy consumption in an ideal state. For example, patent CN103819995B provides a simple method for preparing a superhydrophobic functional coating, which consists of inorganic nanoparticles and an organic solvent, and has good hydrophobic effect by spray molding, but in practical application, the superhydrophobic coating has low strength and poor wear resistance, and the micron/nanoscale layered structure is extremely easy to be damaged, resulting in coating failure [ Zhan Xiaoli, etc., chinese patent CN103819995B ]. Patent CN113663891A provides a flexible repairable super-hydrophobic membrane and a preparation method thereof, provides a certain mechanical property of a coating, and ensures that the coating has certain self-repairing capability [ Xing Suli, chinese patent CN113663891A ]. However, the anti-icing coating is a passive anti-icing technology which cannot be manually interfered, and can only delay icing to a certain extent. The surface micro/nano configuration of the coating is easy to lose effectiveness, the coating loses super-hydrophobicity and is frozen, the surface is covered by ice, the super-hydrophobic effect is lost, the ice layer is rapidly accumulated, and the ice cannot be actively removed [ Huang X, tepylo N, pommier-Budinger V, et al A survey of icephobic coatings and their potential use in a hybrid coating/active ice protection system for aerospace applications, progress in Aerospace Sciences 105 (2019) 74-97 ]. The limited efficiency and the insufficient reliability of the anti-icing surface lead to the great limitation of the application of the anti-icing surface, and the anti-icing surface is not applied to the large-scale application in the industries of aircrafts, wind power and electric power transmission.
Therefore, development of an anti-icing/deicing technology is needed, the technical problems of high energy consumption and low energy efficiency are overcome on the basis of safety and reliability, the electric heating and super-hydrophobic coating technology is combined, the electric energy consumption is reduced by means of hydrophobicity of the coating, the energy efficiency is improved, and the safe and reliable anti-icing/deicing effect is ensured by means of the electric heating capability of the coating.
Patent CN105032731a provides an energy-saving anti-icing/deicing coating with a super-hydrophobic coating and a heating coating being composited in multiple layers, and the heating coating is sprayed with an anti-icing coating so as to combine the two coatings, thereby improving heating efficiency and realizing energy-saving icing [ Chen Huawei, etc., chinese patent CN105032731a ]. However, in the multi-layered structure, the heating layer and the anti-icing layer are separately prepared, which is disadvantageous in that: firstly, the multilayer structure generates redundant thermal resistance, and the heat transfer efficiency is low; secondly, different functional layers have higher thermal mismatch and thermal stress in service, and delamination and falling failure are easy to generate; furthermore, the preparation process has more steps and is more complex. Patent CN109111848A provides a preparation method of carbon fiber composite silicone rubber electrothermal super-hydrophobic coating, which is to composite modified carbon fiber with silicone rubber coating, and use a coating, and simultaneously make the coating have the power generation capacity and micro-nano configuration, good heating and hydrophobic properties, and the coating has the functions of delaying icing and melting ice in low-temperature environment [ He Yunhua, etc., chinese patent CN109111848A ]. However, the preparation process utilizes high pressure, plasma gas and other technologies to construct the coating surface with a water contact angle of about 140-150 degrees, and the preparation process is complex in process, high in cost and not provided with stable superhydrophobicity.
Disclosure of Invention
The utility model aims to provide a superhydrophobic electrothermal anti-icing/deicing coating material and a preparation method thereof, wherein the coating uses carbon fiber and conductive nano material to form a micro/nano composite conductive functional body, uses a low surface energy polymer as a matrix and covers an icing protection surface, uses a material system, constructs an electrothermal system with a superhydrophobic micro/nano structure on the surface in a single-layer coating structure, simultaneously realizes fusion of two anti-icing/deicing mechanisms of electrothermal and superhydrophobic, reduces electrothermal energy consumption and improves energy efficiency by virtue of hydrophobicity of the coating, ensures safe and reliable anti-icing effect by virtue of electrical heating capability of the coating, breaks through the defects of high long-term operation energy consumption, insufficient reliability and incapacity of deicing of the traditional electrothermal anti-icing/deicing coating, and is a reliable, efficient and low-consumption anti-icing method.
The aim of the utility model can be achieved by the following technical scheme: the super-hydrophobic electrothermal anti-icing/deicing coating comprises the following raw materials in parts by weight: 50-100 parts of low-surface-energy high-molecular material, 10-30 parts of carbon fiber and 5-40 parts of nano material. The low surface energy polymer material refers to a solid with low surface energy (usually lower than 35 mJ/m) 2 ) A hydrophobic polymer material with a static water contact angle greater than 90 degrees, comprising: one or a mixture of a plurality of Polydimethylsiloxane (PDMS), polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF) and copolymers thereof, polyurethane (PU), epoxy resin and the like, wherein the diameter of the carbon fiber is 1-100 mu m, the length of the carbon fiber is 20-1000 mu m, and the conductive nano material comprises: the nanometer carbon material is one or more of carbon nanotube, carbon nanometer fiber, carbon nanometer sphere, nanometer carbon black, nanometer metal oxide, nanometer silver, nanometer aluminum, nanometer copper, nanometer iron, nanometer tin dioxide, nanometer ferroferric oxide, etc.
The utility model provides a low-cost preparation method of a superhydrophobic electrothermal anti-icing/deicing coating material, which comprises the following steps:
(1) Weighing 10-30 parts of carbon fiber according to a proportion, and stirring after performing ultrasonic dispersion for 10-30min in 5-40 parts of conductive nano material in a good solvent of a low-surface-energy high polymer material (comprising one or a mixture of more of ethyl acetate, normal hexane, cyclohexanone, acetone, butanone, dimethylbenzene, toluene and the like), wherein the rotating speed of a rotor is 800-1000r/min, and the mixing time is 2-10min.
(2) Weighing 50-100 parts of low surface energy polymer material according to a proportion, adding the low surface energy polymer material into the solution dispersed in the step (1) for high-speed uniform mixing, wherein the rotating speed of a rotor is 1000-1400r/min, and the mixing time is 2-10min, so that the obtained low surface energy polymer material/carbon fiber/conductive nano material solution is the super-hydrophobic electrothermal anti-icing/deicing coating material.
(3) Adding a curing agent of the low-surface-energy polymer material (which is selected from curing agents corresponding to the low-surface-energy polymer material commonly used in the field) into the uniformly mixed low-surface-energy polymer material/carbon fiber/conductive nanomaterial solution obtained in the step (2) according to a proportion, and uniformly mixing; the rotating speed of the rotor is 1000-1400r/min, and the mixing time is 2-10min. The curing agent and the used high polymer material are matched, and are commercially available, for example, the most commonly used commercial PDMS (polydimethylsiloxane) of the Dow Corning PDMS184 comprises two bottles of AB, generally called B as the curing agent, and the ratio of the B to the B is 10:1 for curing; the curing agents required for PU are generally referred to as crosslinking agents.
(4) And (3) sticking copper foil serving as an electrode on two sides of the surface of the substrate by using high-temperature resistant conductive adhesive (the high-temperature conductive adhesive is commonly used in the field) and uniformly mixing the coating, coating the substrate, curing at a high temperature of 80-120 ℃ for 120-360min.
The utility model provides a super-hydrophobic electrothermal anti-icing/deicing coating material, which is formed by carbon fiber and conductive nano material to form a micro/nano composite conductive functional body, and a low surface energy polymer is used as a matrix to cover an icing protection surface. The carbon fibers form the main body of the conductive network; the conductive nano material has two important functions, namely, the conductive nano material is lapped between carbon fibers to form a conductive functional network, and a fine micro/nano structure is constructed on the surface to provide hydrophobicity for the coating; the low surface energy polymer is used as a film forming substance of the coating, so that the coating has enough strength, environmental resistance and processing and forming properties, an electrothermal network with a super-hydrophobic micro/nano structure is built on the surface in a single-layer coating structure by using a material system, and meanwhile, the fusion of two anti-icing/deicing mechanisms of electrothermal and super-hydrophobic is realized, the electrothermal energy consumption is reduced by means of the hydrophobicity of the coating, the energy efficiency is improved, the safe and reliable anti-icing effect is ensured by means of the electrothermal capability of the coating, and meanwhile, the defects of high energy consumption, low energy consumption and insufficient safety and reliability of practical application of the electrothermal anti-icing/deicing technology with the super-hydrophobic coating are overcome. Meanwhile, the coating avoids the problems of interface thermal resistance, easy debonding and cracking due to interface thermal mismatch and the like of the multi-layer coating, enhances the performance reliability and improves the anti-icing/deicing energy rate and efficiency.
Compared with the prior art, the utility model has the beneficial effects that:
(1) The utility model combines the electric heating and super-hydrophobic coating technology, reduces the electric heat energy consumption by depending on the hydrophobicity of the coating, improves the energy efficiency, ensures the safe and reliable anti-icing/deicing effect by depending on the electric heating capacity of the coating, and breaks through the technical problems of high energy consumption and easy failure of the traditional electric heating coating after ice coating.
(2) The material disclosed by the utility model is used for constructing a super-hydrophobic conductive network, carbon fibers are used for forming a main body of the conductive network, and the conductive nano material is used for constructing a fine/nano structure on the surface of the carbon fibers to provide hydrophobicity and simultaneously is used as a bridge between the overlapping carbon fibers to jointly construct the conductive network. An electrothermal system with a super-hydrophobic micro/nano structure on the surface is formed by using one coating, two mechanisms are formed in a single-layer coating structure at the same time, the system has good compatibility, high binding force, no interface performance and additional heat resistance, and is not easy to peel off, and the anti-icing/deicing reliability is improved.
(3) Compared with the preparation method, the superhydrophobic electrothermal anti-icing/deicing coating material prepared by the utility model has the advantages of simple flow and easiness in industrial mass production.
Drawings
FIG. 1 is a sample coated with the present superhydrophobic electrothermal anti-icing coating material;
FIG. 2 is a scanning electron microscope image of the super-hydrophobic electrothermal anti-icing coating material, wherein the conductive nanomaterial grows on the surface of carbon fibers and is used as a bridge between overlapping carbon fibers while constructing a surface micro/nano configuration, so that a conductive network is constructed together;
FIG. 3 is a schematic view of the static contact angle of a sample coated with the present superhydrophobic electrothermal anti-icing/deicing coating material, with water as the medium and 153.3℃contact angle, showing superhydrophobicity;
fig. 4 is an electrical heating thermal imaging schematic of a sample coated with the present superhydrophobic electrothermal ice protection/detachment coating material, having a maximum temperature of 170.1 ℃, exhibiting electrical heating capabilities.
FIG. 5 is an electrical heating deicing test of a sample coated with the present superhydrophobic electrothermal anti-icing coating material, water is dyed with pigment, and ice layer thickness is 3mm, it can be observed that 60s ice has melted a portion, and the ice layer has completely melted at 240s, showing excellent electrical heating thickness ice deposition removal capability.
Detailed Description
The present utility model will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present utility model, but are not intended to limit the utility model 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 utility model.
The low surface energy polymer material, the carbon fiber and the nano material adopted by the utility model are commercial products, and have no special requirements.
The following are more detailed embodiments, by which the technical solutions of the utility model and the technical effects that can be obtained are further illustrated.
Example 1
10g of carbon fiber and 40g of carbon nano tube are weighed, dispersed in 80g of solvent ethyl acetate for 20min by ultrasonic, stirred by a magnetic stirring table, and the rotating speed of a rotor is 1000r/min, and the mixing time is 10min. 100g of PDMS is weighed and added into the well dispersed solution for high-speed uniform mixing, the rotating speed of a rotor is 1400r/min, and the mixing time is 10min. And adding a curing agent of PDMS into the uniformly mixed PDMS/carbon fiber/conductive nano material solution, wherein the rotating speed of a rotor is 1400r/min, and the mixing time is 10min. And (3) sticking copper foils on two sides of the surface of the substrate by using high-temperature-resistant conductive adhesive as electrodes, coating the substrate with uniformly mixed paint, curing at a high temperature of 120 ℃ for 120min, and obtaining the superhydrophobic electrothermal anti-icing/deicing coating.
The properties of the resulting superhydrophobic electrothermal anti-icing/deicing coating are shown in table 1.
Example 2
Weighing 20g of carbon fiber and 30g of carbon nanospheres, performing ultrasonic dispersion in 70g of solvent acetone for 15min, and stirring by using a magnetic stirring table, wherein the rotating speed of a rotor is 1000r/min, and the mixing time is 5min. 90g of PU is weighed and added into the well dispersed solution for high-speed uniform mixing, the rotating speed of a rotor is 1200r/min, and the mixing time is 5min. Adding a PU cross-linking agent into the uniformly mixed PU/carbon fiber/conductive nano material solution, wherein the rotating speed of a rotor is 1200r/min, and the mixing time is 5min. And (3) sticking copper foils on two sides of the surface of the substrate by using high-temperature-resistant conductive adhesive as electrodes, coating the substrate with uniformly mixed paint, curing at a high temperature of 120 ℃ for 150min, and obtaining the superhydrophobic electrothermal anti-icing/deicing coating.
The properties of the resulting superhydrophobic electrothermal anti-icing/deicing coating are shown in table 1.
Example 3
15g of carbon fiber and 10g of nano copper are weighed, are subjected to ultrasonic dispersion in 60g of solvent toluene for 10min, and are stirred by a magnetic stirring table, wherein the rotating speed of a rotor is 800r/min, and the mixing time is 10min. 80g of epoxy resin is weighed and added into the well-dispersed solution for high-speed uniform mixing, the rotating speed of a rotor is 1000r/min, and the mixing time is 10min. And adding a curing agent of the epoxy resin into the uniformly mixed epoxy resin/carbon fiber/conductive nano material solution, wherein the rotating speed of a rotor is 1000r/min, and the mixing time is 10min. And (3) sticking copper foils on two sides of the surface of the substrate by using high-temperature-resistant conductive adhesive as electrodes, coating the substrate with uniformly mixed paint, curing at a high temperature of 80 ℃ for 360min, and obtaining the superhydrophobic electrothermal anti-icing/deicing coating.
The properties of the resulting superhydrophobic electrothermal anti-icing/deicing coating are shown in table 1.
Example 4
18g of carbon fiber and 10g of nano ferroferric oxide are weighed, are subjected to ultrasonic dispersion in 50g of solvent n-hexane for 20min, and are stirred by a magnetic stirring table, wherein the rotating speed of a rotor is 1000r/min, and the mixing time is 5min. 50g of PDMS is weighed and added into the well dispersed solution for high-speed uniform mixing, the rotating speed of a rotor is 1200r/min, and the mixing time is 8min. And adding a curing agent of PDMS into the uniformly mixed PDMS/carbon fiber/nano material solution, wherein the rotating speed of a rotor is 1200r/min, and the mixing time is 8min. And (3) sticking copper foils on two sides of the surface of the substrate by using high-temperature-resistant conductive adhesive as electrodes, coating the substrate with uniformly mixed paint, curing at a high temperature of 100 ℃ for 240min, and obtaining the superhydrophobic electrothermal anti-icing/deicing coating.
The properties of the resulting superhydrophobic electrothermal anti-icing/deicing coating are shown in table 1.
Comparative example 1
Preparing a super-hydrophobic electrothermal coating with a multilayer structure: uniformly coating high-temperature-resistant carbon fiber conductive gel on a substrate, and sticking aluminum foils at two ends of the gel surface as electrodes to prepare a bottom conductive layer; the carbon fiber and the conductive nano material in the embodiment are replaced by nano silicon dioxide particles serving as micro/nano configuration particles on the surface of the conductive layer, and the rest is the same as that in the embodiment 1, namely 50g of nano silicon dioxide particles and 100g of PDMS are uniformly mixed, coated and cured to prepare the top layer super-hydrophobic coating, so that the super-hydrophobic electric heating coating with a multilayer structure is obtained.
Comparative example 2
Preparation of polyvinyl alcohol (PVA) with non-Low surface energy Polymer materials (surface energy typically higher than 35mJ/m 2 Hydrophilic polymer material with static water contact angle less than 90 °) as film forming substance: a coating was prepared in the same manner as in example 1.
Comparative example 3
Preparing a coating containing carbon fibers and no conductive nanoparticles: namely, 10g of carbon fiber was used instead of the carbon fiber and carbon nanotube in example 1, and the rest was the same as in example 1 to prepare a coating layer.
Comparative example 4
Preparing a coating containing conductive nanoparticles and no carbon fibers: that is, 40g of carbon nanotubes were used instead of the carbon fibers and carbon nanotubes in example 1, and the rest was the same as in example 1 to prepare a coating layer.
The effect of the coatings prepared in each example and comparative example was tested by the following test method:
1. the static contact angle of the sample is measured by a static contact angle measuring instrument, and the medium is water.
2. After the surface of the coating was polished 1000 times by 200-mesh sand paper, the static contact angle of the sample was measured using a static contact angle measuring instrument, and the medium was water.
3. The coating is placed in an environment of minus 30 ℃, water drops are dropped on the surface of the coating, a camera is used for recording the state change of the water drops, when the water drops are changed into complete opacity, the water drops are completely frozen, and the delay icing time is recorded.
4. And (3) placing the coating in an environment of minus 30 ℃, dripping water drops on the surface of the coating, electrifying and heating the coating when the water drops are completely frozen at a certain rated power, and recording the melting time of the ice drops when the ice drops are completely opaque and transparent.
5. The coating is placed in an environment with the room temperature of 15 ℃ and is electrified and heated with certain rated power, and when the temperature of the coating tends to be stable, the highest temperature reached by the surface energy of the coating is recorded.
The results of the performance tests are shown in table 1 below:
TABLE 1
As can be seen from 4 examples of table 1, the superhydrophobic electrothermal anti-icing/deicing coating prepared by the present utility model has a static water contact angle of greater than 150 °, i.e., superhydrophobicity. After being sanded, the static water contact angle of the surface of the coating is still about 150 degrees, and good hydrophobicity is maintained, so that the coating has certain mechanical strength and excellent wear resistance. In a low-temperature environment of minus 30 ℃, under the condition of no power on, the anti-icing performance is excellent only by virtue of the superhydrophobicity of the coating, water drops are completely frozen after being dropped on the surface of the coating for about one hour, the icing delay time is long, namely the electric heating window required for anti-icing is short, and the energy consumption is low. In a low-temperature environment of minus 30 ℃, water drops frozen on the surface of the coating after 9 seconds on average are completely melted, and the temperature can be raised to about 170 ℃ at the maximum at room temperature and stabilized at the temperature platform. With the combination of figure 4, the surface of the coating under thermal imaging has even heating and no obvious hot spot, which indicates that the internal structure of the coating successfully builds a complete conductive network system. The experimental phenomena of fast temperature rise, high temperature platform and uniform heating prove that the coating has excellent electrothermal capability, and then is converted into reliable deicing performance.
In combination with the comparison of comparative example 1, the superhydrophobic electrothermal coating with a multilayer structure has no great difference in hydrophobic property and a single-layer structure, and has a high static water contact angle and a high icing delay time. After sanding, the micro/nano particles with hydrophobicity are provided as a top layer to be adhered on the electric heating layer, so that the bonding force between interfaces is insufficient, the micro/nano particles are extremely easy to peel off the surface, the contact angle is rapidly reduced, the hydrophobicity is greatly reduced, and the anti-icing performance is reduced. In addition, the time required for melting the ice beads of the multilayer structure in the low-temperature environment of minus 30 ℃ is long, the highest temperature which can be reached on the surface at room temperature is obviously low, the thermal resistance of the interface is obviously reflected to inhibit the heat conduction of the electrothermal functional layer to the surface of the coating, and the energy is additionally lost. Therefore, the coating with a single-layer structure can reach the temperature required by preventing and removing ice more quickly by electrifying and heating under the same rated power, and the energy consumption is low and the energy efficiency is high.
The use of non-low surface energy polymeric materials significantly reduces the abrasion resistance of the coating in combination with the control of comparative example 2. The micro/nano structure constructed by the conductive nano particles on the surface of the coating provides certain hydrophobicity for the coating, and the water contact angle of the surface of the coating is still close to 150 degrees even though the film forming substance is hydrophilic. After the abrasive paper rubs, the surface micro/nano structure is damaged to a certain extent, the contact area of the film forming substance and water drops is increased, so that the static water contact angle is suddenly reduced, and the anti-icing performance is poor. It is expected that when the micro/nano structure of the surface is completely destroyed, the surface of the coating is converted from hydrophobic to hydrophilic, which not only does not play a role in anti-icing, but also promotes the occurrence of icing and increases the consumption of electrothermal deicing, so that the low-surface energy polymer is selected as a film forming material to be a basic stone for ensuring the anti-icing/deicing performance.
In combination with the comparison of comparative example 3, no conductive nanomaterial is added to construct a good surface micro/nano structure, so that the surface of the coating has common hydrophobicity and poor anti-icing performance; meanwhile, no conductive nano material is used as a bridge for overlapping the carbon fibers, a continuous smooth conductive network cannot be formed in the structure only by the carbon fibers, and the deicing performance is poor. In combination with the comparison of comparative example 4, the coating without carbon fiber is basically difficult to electrify the network, has poor electrothermal performance and insufficient deicing performance although a good surface micro/nano structure is constructed. Therefore, the existence of the conductive nano material and the carbon fiber is inexhaustible and complements each other, and a micro/nano composite functional body with super-hydrophobic and electrothermal properties is constructed.
In a comprehensive view, the super-hydrophobic electrothermal anti-icing/deicing coating material prepared by the utility model is in a single-layer structure, has super-hydrophobicity, excellent electrothermal capability and certain wear resistance, and ensures the safe, reliable, efficient and energy-saving anti-icing/deicing performance.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present utility model. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present utility model. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present utility model is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present utility model.
Claims (10)
1. The super-hydrophobic electrothermal anti-icing/deicing coating material is characterized by comprising the following components in parts by weight:
50-100 parts of low-surface-energy high-molecular material;
10-30 parts of carbon fiber;
5-40 parts of conductive nano material.
2. The superhydrophobic electrothermal ice/fire protection coating material according to claim 1, wherein the low surface energy polymer material is solid surface energy lower than 35mJ/m 2 A polymer material with a static water contact angle of more than 90 degrees.
3. A superhydrophobic electrothermal ice protection/deicing coating material according to claim 1 or 2, wherein said low surface energy polymeric material comprises: polydimethylsiloxane (PDMS), polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF) and copolymers thereof, polyurethane (PU) and epoxy resin or the mixture of a plurality of the two.
4. The superhydrophobic electrothermal ice/fire protection coating material according to claim 1, wherein the carbon fiber has a diameter of 1 μm to 100 μm and a length of 20 μm to 1000 μm.
5. The superhydrophobic electrothermal ice/fire protection coating material according to claim 1, wherein the conductive nanomaterial comprises: nanocarbon materials, nanometals or nanometal oxides.
6. The superhydrophobic electrothermal ice/fire protection coating material according to claim 5, wherein the nano carbon material comprises carbon nanotubes, carbon nanofibers, carbon nanospheres, and carbon nanocapsules,
the nano metal comprises nano silver, nano aluminum, nano copper and nano iron;
the nano metal oxide comprises nano tin dioxide or nano ferroferric oxide.
7. A method for preparing a superhydrophobic electrothermal ice/fire protection coating material according to claim 1, comprising the steps of:
(1) Weighing 10-30 parts of carbon fibers according to a proportion, performing ultrasonic dispersion on 5-40 parts of conductive nano materials in a good solvent of a low-surface-energy high-molecular material for 10-30min, and stirring, wherein the rotating speed of a rotor is 800-1000r/min, and the mixing time is 2-10min;
(2) Weighing 50-100 parts of low surface energy polymer material according to a proportion, adding the low surface energy polymer material into the well-dispersed solution obtained in the step (1), and uniformly mixing at a high speed, wherein the rotating speed of a rotor is 1000-1400r/min, and the mixing time is 2-10min; obtaining the super-hydrophobic electrothermal anti-icing/deicing coating material.
8. The method for preparing a superhydrophobic electrothermal anti-icing/deicing coating material according to claim 7, wherein a curing agent is added into the superhydrophobic electrothermal anti-icing/deicing coating material, and the superhydrophobic electrothermal anti-icing/deicing coating is obtained by coating the superhydrophobic electrothermal anti-icing/deicing coating material on a substrate and curing at high temperature.
9. The method for preparing the superhydrophobic electrothermal ice/preventing coating material according to claim 8, wherein the curing agent is a curing agent of a low-surface-energy high polymer material, the high-temperature curing temperature is 80-120 ℃, and the curing time is 120-360min.
10. The method for preparing a superhydrophobic electrothermal ice protection/removal coating material according to claim 7, wherein the good solvent of the low surface energy polymer material in the step (1) comprises: ethyl acetate, n-hexane, cyclohexanone, acetone, butanone, dimethylbenzene and toluene.
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