Polar region ship anti-icing coating capable of adjusting ice adhesive force and preparation method

Abstract

The invention discloses a polar region ship anti-icing coating capable of adjusting ice adhesive force and a preparation method, and belongs to the field of ship surface anti-icing. Comprising a double-layer coupling structure composed of primer and finish paint, and the coverage area of the finish paint on the primer is dynamically controllable; the primer has a super-smooth surface, and the surface microstructure of the primer prevents ice crystals from being embedded into the microstructure by latching lubricating oil; the finish paint is a super-hydrophobic surface obtained by directionally screening and removing magnetic particles in finish paint coating, the micro-area distribution of the super-hydrophobic surface and the removed magnetic particles are in a complementary form in spatial arrangement, and the regulation and control of the exposed area of the primer on the super-smooth surface are realized by controlling the spatial distribution of the magnetic particles. According to the invention, the contradictory problem that a single coating cannot give consideration to'anti-icing 'and'low adhesion' is solved.

Description

Technical Field

[0001] The invention belongs to the field of ship surface anti-icing, and in particular relates to a polar ship anti-icing coating with adjustable ice adhesion and a preparation method thereof. Background Art

[0002] Ice formation is very common in life, but ice formation on ships can seriously affect the navigation safety of ships. Under icing climate conditions, seawater splashing against the hull and supercooled atmospheric water droplets condensing on the surface of the ship can easily cause ice to form on the surface of the ship. Ice formation will not only seriously affect the basic functions of polar ships, but also increase the draft and center of gravity of the ship, affecting the stability of the ship. In addition, the freezing of salty seawater on radio communication equipment and radar will change its dielectric constant and affect the sending and receiving of signals. Therefore, how to effectively prevent polar ships from icing is one of the important technical challenges currently facing polar ships.

[0003] At present, ship anti-icing technology can be divided into two types: super-hydrophobic coating anti-icing and super-slippery coating anti-icing. The specific problems are: although the super-hydrophobic surface can delay surface ice formation, when the super-hydrophobic surface freezes, ice crystals will be embedded in the microstructure of the super-hydrophobic surface, greatly increasing the adhesion of the ice; the super-slippery surface can greatly reduce the adhesion of ice, but it cannot prevent ice formation, and the oil film on its surface will quickly disappear under the erosion of long-term rain and waves, losing the super-slippery effect.

[0004] It can be seen that the current anti-icing coating cannot solve the problems of delaying icing and reducing ice adhesion at the same time, and cannot achieve the regulation of ice adhesion. Therefore, it is urgent to invent a coating that is simple to prepare, has strong applicability, and can both delay icing and reduce ice adhesion after icing. Summary of the invention

[0005] Technical issues to be solved: In order to avoid the shortcomings of the prior art, the present invention provides a polar ship anti-icing coating with adjustable ice adhesion and a preparation method. The anti-icing coating couples a topcoat with super-hydrophobic properties and a primer with super-slip properties. The super-hydrophobic topcoat delays icing, and the super-slip primer reduces ice adhesion, thereby solving the contradictory problem that a single coating cannot take into account both "anti-icing" and "low adhesion". At the same time, the coating reaction of iron powder particles and ammonium carbonate is utilized, combined with the electromagnet directional adsorption technology, to accurately control the particle distribution in the topcoat, ensure the uniformity of the coating, and ensure the dynamic regulation of the exposed area of ​​the super-slip primer, which can be suitable for different environmental requirements.

[0006] The technical solution of the present invention is: an anti-icing coating for polar ships with adjustable ice adhesion, comprising a double-layer coupling structure consisting of a primer and a topcoat, wherein the coverage area of ​​the topcoat on the primer is in a dynamically controllable form; The primer has an ultra-slip surface, and its surface microstructure prevents ice crystals from embedding into the microstructure by locking lubricating oil; The topcoat is a superphobic surface obtained by directional screening and removal of magnetic particles in the topcoat coating. The micro-area distribution of the superphobic surface is complementary to the removed magnetic particles in spatial arrangement. The exposed area of ​​the supersmooth surface primer is regulated by controlling the spatial distribution of the magnetic particles.

[0007] A further technical solution of the present invention is that the primer is a super-slip layer of microstructure filled with lubricating oil formed by a primer coating sprayed on the surface of the substrate, and the primer coating is a mixture of polydimethylsiloxane, dichloromethane, dimethyl silicone oil and a silane coupling agent. A further technical solution of the present invention is: the topcoat is a super-hydrophobic surface that covers part of the primer and is formed by heating the topcoat coating sprayed on the primer surface, so that part of the primer is exposed; the topcoat coating is composed of super-hydrophobic particles, iron powder particles wrapped by ammonium carbonate crystals, and ethanol.

[0008] A further technical solution of the present invention is: the spraying thickness of the primer coating is 20 microns, and the spraying thickness of the topcoat coating is 10 microns.

[0009] A further technical solution of the present invention is: a method for adjusting the coverage area of ​​the topcoat on the primer: The super-hydrophobic particles in the topcoat coating were determined to be 10-micron-sized porous silica particles; Set the exposed area ratio of the primer as needed and use the following formula to calculate the iron powder particle diameter:

[0010] in, is the primer exposed area ratio, is the diameter of porous silica particles, is the diameter of iron powder particles; The mass ratio of porous silica particles to iron powder particles is calculated based on the density ratio of porous silica particles to iron powder particles, and a topcoat coating is prepared according to the obtained mass ratio, thereby obtaining an anti-icing coating with the coverage area of ​​the topcoat on the primer controlled as needed.

[0011] A method for preparing an anti-icing coating for polar ships with adjustable ice adhesion, the specific steps are as follows: Preparation of topcoat coating: super-hydrophobic particles, iron powder particles wrapped by ammonium carbonate crystals, and ethanol are mixed and stirred at room temperature, and then subjected to ultrasonic dispersion treatment to obtain topcoat coating; wherein the super-hydrophobic particles and the iron powder particles wrapped by ammonium carbonate crystals are used as solute particles, ethanol is used as solvent, and the mass ratio of solute particles to solvent is 2:5; Preparation of primer coating: polydimethylsiloxane, dichloromethane and dimethyl silicone oil are mixed and stirred at room temperature, and then subjected to ultrasonic dispersion treatment to obtain a coating precursor liquid, and the coating precursor liquid is mixed and stirred with a silane coupling agent to obtain a primer coating; The primer is sprayed on the surface of the substrate and dried at 60 degrees Celsius for 15 minutes to obtain a semi-cured primer; The topcoat is sprayed on the semi-cured primer surface, and then heated and cured and cooled to room temperature; during the heating process, the ammonium carbonate crystals coated on the surface of the iron powder particles volatilize, exposing the iron powder particles; The exposed iron powder particles are sucked out by an electromagnet, so that the primer at the position where the iron powder particles are located is exposed, thereby obtaining an anti-icing coating with a double layer coupling of primer and topcoat.

[0012] A further technical solution of the present invention is: the specific steps of preparing the topcoat coating are as follows: The surface of porous silica particles is etched with a sodium hydroxide solution to form silica particles with nanoscale micro-surface structures; The silicon dioxide particles with nano-scale micro-surface structures are subjected to low surface energy treatment to obtain silicon dioxide nanoparticles with amphiphobic properties, i.e., superhydrophobic particles; preparing iron powder particles coated with ammonium carbonate crystals; The silicon dioxide nanoparticles with amphiphobic properties, the iron powder particles wrapped by ammonium carbonate crystals and ethanol are mixed and stirred at room temperature, and then subjected to ultrasonic dispersion treatment at room temperature to obtain a topcoat coating.

[0013] A further technical solution of the present invention is: the preparation method of the iron powder particles wrapped by ammonium carbonate crystals is as follows: The iron powder particles, ammonium carbonate and water were stirred uniformly in a water bath heated at 35 degrees Celsius, and then ultrasonically dispersed to obtain a mixed solution; wherein the mass ratio of the iron powder particles, ammonium carbonate and water was 3:5:60; The mixed solution after dispersion treatment is further cooled to 15 degrees Celsius at a cooling rate of 1 degree Celsius per minute under an ultrasonic dispersion environment; The mixed solution after the cooling treatment is stirred by an electromagnet, and the particles adsorbed by the electromagnet are the iron powder particles wrapped by the ammonium carbonate crystals.

[0014] A further technical solution of the present invention is: in the preparation process of the primer coating, the mass ratio of polydimethylsiloxane, dichloromethane, dimethyl silicone oil and silane coupling agent is 10:20:8:1.

[0015] A further technical solution of the present invention is: the topcoat is sprayed on the semi-cured primer surface, and the heating and curing process is to increase the temperature from 95°C to 150°C within 30 minutes and maintain the temperature at 150°C for 10 minutes. Beneficial Effects The beneficial effects of the present invention are: the present invention realizes the efficient synergy of anti-icing and low adhesion through the partially covered double-layer coupling structure and preparation process, and has the characteristics of superior performance, flexible preparation and low cost, and provides a breakthrough solution for anti-icing technology in the fields of polar ships, aerospace equipment, etc. The specific advantages are analyzed as follows: 1. The present invention combines the super-hydrophobic topcoat to delay surface icing and the super-slip primer to reduce ice adhesion, achieving the synergistic effect of anti-icing and low adhesion, effectively solving the industry problem that a single coating cannot take into account both "delayed icing" and "low adhesion". Among them, the lubricating oil locked in the primer microstructure is reduced through a mechanical interlocking design, significantly extending the durability of the super-slip performance, and is suitable for polar environments frequently washed by waves.

[0016] 2. The present invention achieves precise control of the primer exposure area by adjusting the diameter ratio of iron powder particles and silica particles, meeting the requirements of polar working conditions with different temperatures, humidity and salt spray concentrations; it is suitable for substrates such as metals and composite materials with different roughness, and can be expanded to multiple fields such as ships, aerospace equipment and high-voltage cables.

[0017] 3. In the preparation process of the present invention, the primer and topcoat are sprayed in stages, combined with low-temperature pre-curing (60°C) and high-temperature final curing (150°C) to ensure strong coating interface bonding and stable structure. Electromagnets are used to accurately adsorb and remove iron powder particles to achieve controllable adjustment of the micro-area distribution on the coating surface, with high process repeatability and simple operation.

[0018] 4. The present invention uses common materials such as polydimethylsiloxane and silicon dioxide, and the spraying process does not require complex equipment, which is suitable for large-scale industrial production. The iron powder particles used can be recycled, reducing waste generation and meeting environmental protection requirements; the coating does not contain controlled chemicals and is environmentally friendly. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 A schematic diagram of the structure of an anti-icing coating for polar ships with adjustable ice adhesion and a schematic diagram of the contact state of droplets on the surface of the anti-icing coating in Example 1 of the present invention; Figure 2 This is a schematic top view of an anti-icing coating for polar ships with adjustable ice adhesion in Example 1 of the present invention; Figure 3The microscopic image of an anti-icing coating for polar ships with adjustable ice adhesion in Example 2 of the present invention; (a) a microscopic image of an anti-icing coating with an exposed surface of a super-slippery primer and an area of ​​a super-repellent topcoat accounting for about 50%; (b) a graph of droplet contact angle test results; Figure 4 The microscopic image of an anti-icing coating for polar ships with adjustable ice adhesion in Example 3 of the present invention; (a) a microscopic image of an anti-icing coating with an exposed surface of a super-slippery primer and an area of ​​a super-repellent topcoat accounting for about 30% and 70%; (b) a droplet contact angle test result image; Figure 5 The microscopic image of an anti-icing coating for polar ships with adjustable ice adhesion in Example 4 of the present invention; (a) a microscopic image of an anti-icing coating with an exposed surface of a super-slippery primer and an area of ​​a super-repellent topcoat accounting for about 60% and 40% respectively; (b) a graph of droplet contact angle test results; Figure 6 Comparison of ice adhesion with different percentages of superhydrophobic surface of topcoats.

[0020] Explanation of reference numerals: 1. substrate; 2. primer; 3. topcoat; 4. droplet. DETAILED DESCRIPTION

[0021] The embodiments described below with reference to the accompanying drawings are exemplary and are intended to be used to explain the present invention, but should not be construed as limiting the present invention.

[0022] At present, ship anti-icing technology can be divided into two types: super-hydrophobic coating anti-icing and super-slippery coating anti-icing. Although the super-hydrophobic surface can delay surface ice formation, when the super-hydrophobic surface freezes, ice crystals will embed into the microstructure of the super-hydrophobic surface, greatly increasing the adhesion of the ice; the super-slippery surface can greatly reduce the adhesion of ice, but it cannot prevent ice formation, and the oil film on its surface will quickly disappear under the erosion of rain and waves for a long time, losing the super-slippery effect.

[0023] For example, a shape memory anti-icing composite film has been disclosed, which solves the problem of increased ice adhesion on super-hydrophobic surfaces after freezing.

[0024] The publicly disclosed ultra-slippery coating with photothermal function adds photothermal function on the basis of ultra-slippery coating, but the use of photothermal function is greatly restricted and it cannot prevent icing on cloudy days.

[0025] The disclosed hydrophilic and hydrophobic anti-icing coating has a hydrophobic part on the surface that makes water slide off the surface easily, while the hydrophilic part can inhibit the freezing of water on the surface and form a water lubricating layer, thus having low adhesion. However, the hydrophilic part is a traditional water film. When the surface is in a low temperature environment for a long time, the surface will freeze, losing the hydrophilic effect, and at the same time increasing the adhesion of ice.

[0026] The disclosed super-hydrophobic anti-icing coating still does not solve the problem that the adhesion of the super-hydrophobic surface increases after freezing.

[0027] The disclosed super-slip coatings do not solve the problem of preventing ice from forming on super-slip surfaces.

[0028] Based on the above problems, the present invention provides a polar ship anti-icing coating with adjustable ice adhesion, including a double-layer coupling structure consisting of a primer and a topcoat, wherein the coverage area of ​​the topcoat on the primer is in a dynamically controllable form; the primer is an ultra-slippery surface, and its surface microstructure prevents ice crystals from embedding into the microstructure by locking lubricating oil; the topcoat is an ultra-phobic surface obtained by directional screening and removal of magnetic particles in the topcoat coating, and the micro-area distribution of the ultra-phobic surface is complementary to the removed magnetic particles in the spatial arrangement, and the exposure area of ​​the primer on the ultra-slippery surface is regulated by controlling the spatial distribution of the magnetic particles.

[0029] Specifically, the primer is a lubricating layer of microstructure filled with lubricating oil formed by a primer coating sprayed on the surface of a substrate, and the primer coating is a mixture of polydimethylsiloxane, dichloromethane, dimethyl silicone oil and a silane coupling agent. Specifically, the topcoat is a super-hydrophobic surface formed by spraying the topcoat coating on the surface of the primer and heating it to cover part of the primer, so that part of the primer is exposed; the topcoat coating is composed of super-hydrophobic particles, iron powder particles wrapped by ammonium carbonate crystals, and ethanol.

[0030] The present invention provides a method for preparing an anti-icing coating for polar ships with adjustable ice adhesion, and the specific steps are as follows: Preparation of topcoat coating: super-hydrophobic particles, iron powder particles wrapped by ammonium carbonate crystals, and ethanol are mixed and stirred at room temperature, and then subjected to ultrasonic dispersion treatment to obtain topcoat coating; wherein the super-hydrophobic particles and the iron powder particles wrapped by ammonium carbonate crystals are used as solute particles, ethanol is used as solvent, and the mass ratio of solute particles to solvent is 2:5; Preparation of primer coating: polydimethylsiloxane, dichloromethane and dimethyl silicone oil are mixed and stirred at room temperature, and then subjected to ultrasonic dispersion treatment to obtain a coating precursor liquid, and the coating precursor liquid is mixed and stirred with a silane coupling agent to obtain a primer coating; The primer is sprayed on the surface of the substrate and dried at 60 degrees Celsius for 15 minutes to obtain a semi-cured primer; The topcoat is sprayed on the semi-cured primer surface, and then heated and cured and cooled to room temperature; during the heating process, the ammonium carbonate crystals coated on the surface of the iron powder particles volatilize, exposing the iron powder particles; The exposed iron powder particles are sucked out by an electromagnet, so that the primer at the position where the iron powder particles are located is exposed, thereby obtaining an anti-icing coating with a double layer coupling of primer and topcoat.

[0031] In summary, the adhesion of traditional super-hydrophobic coatings increases sharply after ice formation, while the present invention significantly reduces the energy consumption of de-icing by exposing the super-slip primer to directly contact the ice layer. Traditional super-slip coatings rely on oil films that are prone to loss, while the present invention improves lubrication durability through micro-structure oil locking and double-layer coupling design.

[0032] The above technical solution is further described below in conjunction with the accompanying drawings: Embodiment 1: Reference Figure 1 and Figure 2 As shown, the present embodiment is a polar ship anti-icing coating with adjustable ice adhesion, which consists of two parts: a primer 2 and a topcoat 3. After the primer 2 is sprayed, the surface of the substrate 1 can be transformed into a super-slip surface. The interior of the surface microstructure is filled with lubricating oil, which can effectively prevent ice crystals from embedding into the microstructure after freezing, thereby reducing the ice adhesion. The topcoat 3 is a super-phobic surface that can effectively prevent liquids from wetting the surface; the topcoat coating is sprayed on the upper layer of the super-slip primer 2, but the super-phobic topcoat 3 does not completely cover the super-slip primer, but has certain gaps, which can expose part of the super-slip primer surface so that it can contact the ice. At the same time, the exposure area of ​​the super-slip primer can be achieved by adjusting the composition of the topcoat; the contact state of the droplets on the surface of the anti-icing coating is as shown in FIG. Figure 1 The present invention has an anti-icing coating with super-hydrophobic top layer and super-slip bottom layer, and solves the preparation problem thereof. The method for preparing a polar ship anti-icing coating with adjustable ice adhesion described in this embodiment comprises the following steps: Step 1: Prepare polydimethylsiloxane, dichloromethane, dimethyl silicone oil, silane coupling agent, 10-micron porous micron silica particles, sodium hydroxide, perfluorotriethoxysilane, ethanol, deionized water, ammonium carbonate and iron powder of different diameter particles (diameters between 0.5 microns and 100 microns) for use.

[0033] Topcoat preparation: Step 2: Prepare a sodium hydroxide solution with a concentration of 5 mol / L, slowly add 10 micron porous silica particles into the sodium hydroxide solution, and react at 95 degrees Celsius for 10 minutes. During this process, the beaker mouth needs to be covered to prevent gas volatilization. After the reaction is completed, silica particles with nano-scale micro-surface structures are obtained. Then the silica particles with nano-scale micro-surface structures are filtered out, ultrasonically cleaned with deionized water for 20 minutes, and placed in an oven for drying for later use.

[0034] In the above process, the surface material of the porous silica particles will react under the action of sodium hydroxide, wherein the surface material of the porous silica particles will continuously react with sodium hydroxide to generate sodium silicate, and fall off from the surface of the porous silica particles, thereby forming a smaller nanoscale microstructure on the surface of the porous silica particles.

[0035] Step 3: Mix perfluorotriethoxysilane and ethanol in a mass ratio of 1:100, add the dried silica particles with nanoscale micro-surface structure, stir at room temperature for 3 hours, then filter it out and dry it in an oven at 120 degrees Celsius for 3 hours to complete the low surface energy treatment, and then obtain silica nanoparticles with amphiphobic properties.

[0036] Step 4: Take iron powder particles, ammonium carbonate and water in a mass ratio of 3:5:60 and add them to a beaker, and stir evenly in a water bath heated at 35 degrees Celsius; then ultrasonically disperse for half an hour, during which the solution temperature is maintained at around 35 degrees Celsius by a water bath method; after half an hour, while continuing to ultrasonically disperse, cool the temperature to 15 degrees Celsius at a cooling rate of 1 degree Celsius per minute, and then place an electromagnet on the side wall of the beaker and stir for about 10 minutes, pour out the particles and solution in the beaker that are not adsorbed by the electromagnet, and the remaining particles adsorbed by the electromagnet are iron powder particles wrapped by ammonium carbonate crystals.

[0037] Step 5: Take a certain mass ratio of iron powder particles wrapped by ammonium carbonate crystals, silicon dioxide nanoparticles with amphiphobic properties and ethanol, stir them with a magnetic stirrer at room temperature of 25 degrees Celsius for 1 hour, and then ultrasonically disperse them at room temperature for 30 minutes, during which the temperature is controlled by a water bath, to obtain a topcoat coating. The solution should be sealed during this process to prevent it from volatilizing.

[0038] It should be noted that in this step, the mass ratio between the solute particles (iron powder particles wrapped by ammonium carbonate crystals and silica nanoparticles with amphiphobic properties) and the solvent (ethanol) is about 2:5, and the ratio between the iron powder particles wrapped by ammonium carbonate crystals and the silica nanoparticles with amphiphobic properties can be adjusted between 1:18 and 5:1 to achieve different coverage area ratios of the primer.

[0039] Primer preparation: Step 6: Take polydimethylsiloxane, dichloromethane and dimethyl silicone oil in a mass ratio of 5:10:4, add them into a beaker in sequence, stir at room temperature for 30 minutes with a magnetic stirrer, cover the beaker with plastic wrap to prevent evaporation, and after stirring, use ultrasonic dispersion for 30 minutes to obtain a coating precursor solution.

[0040] Spray coating: Step seven: Add a silane coupling agent to the coating precursor liquid prepared in step six, wherein the mass ratio of dimethylsiloxane, dichloromethane, dimethyl silicone oil and silane coupling agent is 10:20:8:1, and stir for 15 minutes to obtain a primer coating; use a spray gun to spray the primer coating on the surface of the substrate to be sprayed, and the spraying thickness is controlled between 20 microns, and then put it into an oven at 60 degrees Celsius for 15 minutes to obtain a semi-cured primer.

[0041] Step 8: Spray the topcoat prepared in step 5 onto the semi-cured primer surface with a spraying thickness of 10 microns.

[0042] Step 9: Place the substrate sprayed with primer and topcoat in an oven, increase the temperature from 95 degrees Celsius to 150 degrees Celsius within 30 minutes, maintain 150 degrees Celsius for 10 minutes, then take it out and cool it down to room temperature.

[0043] Step 10: Use an electromagnet to remove the iron powder particles on the surface of the coating prepared in step 9 from the surface of the substrate. At this time, the entire coating is prepared.

[0044] Specifically, the method for adjusting the coverage area of ​​the topcoat on the primer comprises the following steps: The super-hydrophobic particles in the topcoat coating were determined to be 10-micron-sized porous silica particles; Set the exposed area ratio of the primer as needed and use the following formula to calculate the iron powder particle diameter:

[0045] in, is the primer exposed area ratio, is the diameter of porous silica particles, is the diameter of iron powder particles; The mass ratio of porous silica particles to iron powder particles is calculated based on the density ratio of porous silica particles to iron powder particles, and a topcoat coating is prepared according to the obtained mass ratio, thereby obtaining an anti-icing coating with the coverage area of ​​the topcoat on the primer controlled as needed.

[0046] It should be noted that the substrate to be sprayed should have a roughness of R5 to R10 to ensure the adhesion between the primer and the substrate. The diameter of the 10 micron-level porous silica nanoparticles mentioned in step one can be between 5 and 500 microns, and the porous structure is to maintain the roughness of the surface of the silica particles. In step two, the porous silica particles are treated with sodium hydroxide to prepare nanoscale microstructures. Under this parameter, it can be ensured that the silica particles are not excessively corroded, and nanoscale composite microstructures can be produced. While ensuring better super-phobic properties, the adhesion between the primer is stronger. After spraying the primer in step six, it is placed in an oven at 60 degrees Celsius for 15 minutes and then taken out, in order to make it initially formed but not completely solidified. After spraying the topcoat, the silica particles of the topcoat can be trapped in the primer to form a strong mechanical interlocking, and the combination between the back paint and the primer after heating again is more firmly.

[0047] The method mentioned in the present invention is easy to prepare, and the coating only needs to be sprayed, the steps are simple, and it can be widely used in the anti-icing and anti-corrosion of equipment in the fields of aerospace, navigation, etc.

[0048] Embodiment 2: The specific steps for preparing an anti-icing coating with a super-slip primer surface and a super-repellent topcoat area of ​​about 50% on the aluminum surface are as follows: Step 1: prepare polydimethylsiloxane, dichloromethane, dimethyl silicone oil, silane coupling agent, 10-micron porous micron silica particles, sodium hydroxide, perfluorotriethoxysilane, ethanol, deionized water, ammonium carbonate and 10-micron diameter particle iron powder for use.

[0049] Topcoat preparation: Step 2: Prepare a sodium hydroxide solution with a concentration of 5 mol / L, slowly add 10 micron porous silica particles into the sodium hydroxide solution, and react at 95 degrees Celsius for 10 minutes. During this process, the beaker mouth needs to be covered to prevent gas volatilization. After the reaction is completed, silica particles with nano-scale micro-surface structures are obtained. Then the silica particles with nano-scale micro-surface structures are filtered out, ultrasonically cleaned with deionized water for 20 minutes, and placed in an oven for drying for later use.

[0050] In the above process, the surface material of the porous silica particles will react under the action of sodium hydroxide, wherein the surface material of the porous silica particles will continuously react with sodium hydroxide to generate sodium silicate and fall off from the surface of the porous silica particles, thereby forming a smaller nanoscale microstructure on the surface of the porous silica particles. In this process, whether the surface of the porous silica particles can generate a uniform nanostructure has a complex relationship with the concentration of sodium hydroxide, the reaction time, the diameter of the porous silica particles, and the porosity of the porous silica particles, and needs to be operated according to the ratio proposed in this application.

[0051] Step 3: Mix perfluorotriethoxysilane and ethanol in a mass ratio of 1:100, add the dried silica particles with nanoscale micro-surface structure, stir at room temperature for 3 hours, then filter it out and dry it in an oven at 120 degrees Celsius for 3 hours to complete the low surface energy treatment, and then obtain silica nanoparticles with amphiphobic properties.

[0052] Step 4: Take iron powder particles, ammonium carbonate and water in a mass ratio of 3:5:60 and add them to a beaker, and stir evenly in a water bath heated at 35 degrees Celsius; then ultrasonically disperse for half an hour, during which the solution temperature is maintained at around 35 degrees Celsius by a water bath method; after half an hour, cool the solution to 15 degrees Celsius at a cooling rate of 1 degree Celsius per minute during the ultrasonic dispersion process, and then place an electromagnet on the side wall of the beaker and stir for about 10 minutes, pour out the particles and solution in the beaker that are not adsorbed by the electromagnet, and the remaining particles adsorbed by the electromagnet are iron powder particles wrapped by ammonium carbonate crystals.

[0053] Step 5: Take iron powder particles wrapped by ammonium carbonate crystals, silicon dioxide nanoparticles with amphiphobic properties and ethanol in a mass ratio of 1:3.6:11.5, stir them with a magnetic stirrer at room temperature of 25 degrees Celsius for 1 hour, and ultrasonically disperse them at room temperature for 30 minutes, during which the temperature is controlled in a water bath, to obtain a topcoat coating. The solution should be sealed during this process to prevent it from volatilizing.

[0054] Primer preparation: Step 6: Take polydimethylsiloxane, dichloromethane and dimethyl silicone oil in a mass ratio of 5:10:4, add them into a beaker in sequence, stir at room temperature for 30 minutes with a magnetic stirrer, cover the beaker with plastic wrap to prevent evaporation, and after stirring, use ultrasonic dispersion for 30 minutes to obtain a coating precursor solution.

[0055] Spray coating: Step 7: Add silane coupling agent to the coating precursor liquid prepared in step 6, wherein the mass ratio of dimethylsiloxane, dichloromethane, dimethyl silicone oil and silane coupling agent is 10:20:8:1. After stirring for 15 minutes, use a spray gun to spray it on the surface of the substrate to be sprayed. The spraying thickness is controlled at 20 microns, and then put it into an oven and dry it at 60 degrees Celsius for 15 minutes to obtain a semi-cured primer.

[0056] The specific spraying parameters are: the spray gun air pressure is set to 2.8 bar, the spraying height is about 25 cm, the moving speed is about 2 cm / s, the spraying flow rate is 80 ml / min, and the nozzle diameter is 1 mm.

[0057] Step 8: Spray the topcoat prepared in step 5 onto the semi-cured primer surface with a spraying thickness of 10 microns.

[0058] The specific spraying parameters are: the spray gun air pressure is set to 2.8 bar, the spraying height is about 25 cm, the moving speed is about 4 cm / s, the spraying flow rate is 60 ml / min, and the nozzle diameter is 1 mm.

[0059] Step 9: Place the substrate sprayed with primer and topcoat in an oven, increase the temperature from 95 degrees Celsius to 150 degrees Celsius within 30 minutes, maintain 150 degrees Celsius for 10 minutes, then take it out and cool it down to room temperature.

[0060] Step 10: Use an electromagnet to remove the iron powder particles on the surface of the coating prepared in step 9 from the surface of the substrate. At this time, the entire coating is prepared and the coating surface is as follows: Figure 3 shown.

[0061] In this embodiment, the super hydrophobic particles in the topcoat coating are determined to be 10 micron porous silica particles; Set the exposed area ratio of the primer as needed and use the following formula to calculate the iron powder particle diameter:

[0062] in, is the primer exposed area ratio, is the diameter of porous silica particles, is the diameter of the iron powder particles; is 50%, is 10 microns, then the calculation can be obtained is 10 microns.

[0063] According to the density ratio of porous silica particles and iron powder particles of about 1:3.6, the mass ratio of porous silica particles and iron powder particles can be calculated to be 3.6:1. By preparing the topcoat coating according to the obtained mass ratio, an anti-icing coating with the coverage area of ​​the topcoat on the primer controlled as needed can be obtained.

[0064] Depend on Figure 6 It can be seen that when the superhydrophobic topcoat accounts for 50%, the adhesion of surface ice is about 95 kPa.

[0065] Embodiment 3: The specific steps for preparing an anti-icing coating with a super-slip primer surface and a super-repellent topcoat area ratio of about 30%:70% on the substrate surface are as follows: Step 1: prepare polydimethylsiloxane, dichloromethane, dimethyl silicone oil, silane coupling agent, 10-micron porous micron silica particles, sodium hydroxide, perfluorotriethoxysilane, ethanol, deionized water, ammonium carbonate and 6-micron diameter particle iron powder for use.

[0066] Topcoat preparation: Step 2: Prepare a sodium hydroxide solution with a concentration of 5 mol / L, slowly add 10 micron porous silica particles into the sodium hydroxide solution, and react at 95 degrees Celsius for 10 minutes. During this process, the beaker mouth needs to be covered to prevent gas volatilization. After the reaction is completed, silica particles with nano-scale micro-surface structures are obtained. Then filter out the silica particles with nano-scale micro-surface structures, ultrasonically clean them with deionized water for 20 minutes, and put them in an oven to dry for later use.

[0067] In the above process, the surface material of the porous silica particles will react under the action of sodium hydroxide, wherein the surface material of the porous silica particles will continuously react with sodium hydroxide to generate sodium silicate and fall off from the surface of the porous silica particles, thereby forming a smaller nanoscale microstructure on the surface of the porous silica particles. In this process, whether the surface of the porous silica particles can generate a uniform nanostructure has a complex relationship with the concentration of sodium hydroxide, the reaction time, the diameter of the porous silica particles, and the porosity of the porous silica particles, and needs to be operated according to the ratio proposed in this application.

[0068] Step 3: Mix perfluorotriethoxysilane and ethanol in a mass ratio of 1:100, add the dried silica particles with nanoscale micro-surface structure, stir at room temperature for 3 hours, then filter it out and dry it in an oven at 120 degrees Celsius for 3 hours to complete the low surface energy treatment, and then obtain silica nanoparticles with amphiphobic properties.

[0069] Step 4: Take iron powder particles, ammonium carbonate and water in a mass ratio of 3:5:60 and add them to a beaker, and stir evenly in a water bath heated at 35 degrees Celsius; then ultrasonically disperse for half an hour, during which the solution temperature is maintained at around 35 degrees Celsius by a water bath method; after half an hour, cool the solution to 15 degrees Celsius at a cooling rate of 1 degree Celsius per minute during the ultrasonic dispersion process, and then place an electromagnet on the side wall of the beaker and stir for about 10 minutes, pour out the particles and solution in the beaker that are not adsorbed by the electromagnet, and the remaining particles adsorbed by the electromagnet are iron powder particles wrapped by ammonium carbonate crystals.

[0070] Step 5: Take the iron powder particles wrapped by ammonium carbonate crystals prepared in step 4, the silicon dioxide nanoparticles with amphiphobic properties prepared in step 3, and ethanol in a mass ratio of 7.7:10:44.25, stir them with a magnetic stirrer at room temperature of 25 degrees Celsius for 1 hour, and ultrasonically disperse them at room temperature for 30 minutes, during which the temperature is controlled in a water bath. The solution should be sealed during this process to prevent it from volatilizing.

[0071] Primer preparation: Step 6: Take polydimethylsiloxane, dichloromethane and dimethyl silicone oil in a mass ratio of 5:10:4, add them into a beaker in sequence, stir at room temperature for 30 minutes with a magnetic stirrer, cover the beaker with plastic wrap to prevent evaporation, and after stirring, use ultrasonic dispersion for 30 minutes to obtain a coating precursor solution.

[0072] Spray coating: Step 7: Add silane coupling agent to the coating precursor liquid stirred in step 6, wherein the mass ratio of dimethylsiloxane, dichloromethane, dimethyl silicone oil and silane coupling agent is 10:20:8:1. After stirring for 15 minutes, use a spray gun to spray it on the surface of the substrate to be sprayed. The spraying thickness is controlled at 20 microns, and then put it into an oven and dry it at 60 degrees Celsius for 15 minutes to obtain a semi-cured primer.

[0073] The specific spraying parameters are: the spray gun air pressure is set to 2.8 bar, the spraying height is about 25 cm, the moving speed is about 2 cm / s, the spraying flow rate is 80 ml / min, and the nozzle diameter is 1 mm.

[0074] Step 8: Spray the topcoat prepared in step 5 onto the semi-cured primer surface with a spraying thickness of 10 microns.

[0075] The specific spraying parameters are: the spray gun air pressure is set to 2.8 bar, the spraying height is about 25 cm, the moving speed is about 4 cm / s, the spraying flow rate is 60 ml / min, and the nozzle diameter is 1 mm.

[0076] Step 9: Place the substrate sprayed with primer and topcoat in an oven, increase the temperature from 95 degrees Celsius to 150 degrees Celsius within 30 minutes, maintain 150 degrees Celsius for 10 minutes, then take it out and cool it down to room temperature.

[0077] Step 10: Use an electromagnet to remove the iron powder particles on the surface of the coating prepared in step 9 from the surface of the substrate. At this time, the entire coating is prepared and the coating surface is as follows: Figure 4 shown.

[0078] In this embodiment, the super hydrophobic particles in the topcoat coating are determined to be 10 micron porous silica particles; Set the exposed area ratio of the primer as needed and use the following formula to calculate the iron powder particle diameter:

[0079] in, is the primer exposed area ratio, is the diameter of porous silica particles, is the diameter of the iron powder particles; is 30%, is 10 microns, then the calculation can be obtained About 6 microns.

[0080] According to the density ratio of porous silica particles and iron powder particles of about 1:3.6, the mass ratio of porous silica particles and iron powder particles can be calculated to be 10:7.7. By preparing the topcoat coating according to the obtained mass ratio, an anti-icing coating with the coverage area of ​​the topcoat on the primer controlled as needed can be obtained.

[0081] Depend on Figure 6 It can be seen that when the superhydrophobic topcoat accounts for 70%, the adhesion force of surface ice is about 136 kPa.

[0082] Embodiment 4: The specific steps for preparing an anti-icing coating with a super-slip primer surface and a super-repellent topcoat area accounting for approximately 60% and 40% on a substrate are as follows: Step 1: prepare polydimethylsiloxane, dichloromethane, dimethyl silicone oil, silane coupling agent, 10-micron porous micron silica particles, sodium hydroxide, perfluorotriethoxysilane, ethanol, deionized water, ammonium carbonate and 12-micron diameter particle iron powder for use.

[0083] Topcoat preparation: Step 2: Prepare a sodium hydroxide solution with a concentration of 5 mol / L, slowly add 10 micron porous silica particles into the sodium hydroxide solution, and react at 95 degrees Celsius for 10 minutes. During this process, the beaker mouth needs to be covered to prevent gas volatilization. After the reaction is completed, silica particles with nano-scale micro-surface structures are obtained. Then the silica particles with nano-scale micro-surface structures are filtered out, ultrasonically cleaned with deionized water for 20 minutes, and placed in an oven for drying for later use.

[0084] In the above process, the surface material of the porous silica particles will react under the action of sodium hydroxide, wherein the surface material of the porous silica particles will continuously react with sodium hydroxide to generate sodium silicate and fall off from the surface of the porous silica particles, thereby forming a smaller nanoscale microstructure on the surface of the porous silica particles. In this process, whether the surface of the porous silica particles can generate a uniform nanostructure has a complex relationship with the concentration of sodium hydroxide, the reaction time, the diameter of the porous silica particles, and the porosity of the porous silica particles, and needs to be operated according to the ratio proposed in this application.

[0085] Step 3: Mix perfluorotriethoxysilane and ethanol in a mass ratio of 1:100, add the dried silica particles with nanoscale micro-surface structure, stir at room temperature for 3 hours, then filter it out and dry it in an oven at 120 degrees Celsius for 3 hours to complete the low surface energy treatment, and then obtain silica nanoparticles with amphiphobic properties.

[0086] Step 4: Take iron powder particles, ammonium carbonate and water in a mass ratio of 3:5:60 and add them to a beaker, and stir evenly in a water bath heated at 35 degrees Celsius; then ultrasonically disperse for half an hour, during which the solution temperature is maintained at around 35 degrees Celsius by a water bath method; after half an hour, cool the solution to 15 degrees Celsius at a cooling rate of 1 degree Celsius per minute during the ultrasonic dispersion process, and then place an electromagnet on the side wall of the beaker and stir for about 10 minutes, pour out the particles and solution in the beaker that are not adsorbed by the electromagnet, and the remaining particles adsorbed by the electromagnet are iron powder particles wrapped by ammonium carbonate crystals.

[0087] Step 5: Take iron powder particles wrapped by ammonium carbonate crystals, silicon dioxide nanoparticles with amphiphobic properties and ethanol in a mass ratio of 6.2:1:18, stir them with a magnetic stirrer at room temperature of 25 degrees Celsius for 1 hour, and ultrasonically disperse them at room temperature for 30 minutes, during which the temperature is controlled in a water bath to obtain a topcoat coating. The solution should be sealed during this process to prevent it from volatilizing.

[0088] Primer preparation: Step 6: Take polydimethylsiloxane, dichloromethane and dimethyl silicone oil in a mass ratio of 5:10:4, add them into a beaker in sequence, stir at room temperature for 30 minutes with a magnetic stirrer, and cover the beaker with plastic wrap to prevent evaporation. After stirring, use ultrasonic dispersion for 30 minutes to obtain a coating precursor solution.

[0089] Spray coating: Step 7: Add silane coupling agent to the coating precursor liquid stirred in step 6, wherein the mass ratio of dimethylsiloxane, dichloromethane, dimethyl silicone oil and silane coupling agent is 10:20:8:1. After stirring for 15 minutes, use a spray gun to spray it on the surface of the substrate to be sprayed. The spraying thickness is controlled at 20 microns, and then put it into an oven and dry it at 60 degrees Celsius for 15 minutes to obtain a semi-cured primer.

[0090] The specific spraying parameters are: the spray gun air pressure is set to 2.8 bar, the spraying height is about 25 cm, the moving speed is about 2 cm / s, the spraying flow rate is 80 ml / min, and the nozzle diameter is 1 mm.

[0091] Step 8: Spray the topcoat prepared in step 5 onto the semi-cured primer surface with a spraying thickness of 10 microns.

[0092] The specific spraying parameters are: the spray gun air pressure is set to 2.8 bar, the spraying height is about 25 cm, the moving speed is about 4 cm / s, the spraying flow rate is 60 ml / min, and the nozzle diameter is 1 mm.

[0093] Step 9: Place the substrate sprayed with primer and topcoat in an oven, increase the temperature from 95 degrees Celsius to 150 degrees Celsius within 30 minutes, maintain 150 degrees Celsius for 10 minutes, then take it out and cool it down to room temperature.

[0094] Step 10: Use an electromagnet to remove the iron powder particles on the surface of the coating prepared in step 9 from the surface of the substrate. At this time, the entire coating is prepared and the coating surface is as follows: Figure 5 shown.

[0095] In this embodiment, the super hydrophobic particles in the topcoat coating are determined to be 10 micron porous silica particles; Set the exposed area ratio of the primer as needed and use the following formula to calculate the iron powder particle diameter:

[0096] in, is the primer exposed area ratio, is the diameter of porous silica particles, is the diameter of the iron powder particles; is 60%, is 10 microns, then the calculation can be obtained About 12 microns.

[0097] According to the density ratio of porous silica particles and iron powder particles of about 1:3.6, the mass ratio of porous silica particles and iron powder particles can be calculated to be 1:6.2. By preparing the topcoat according to the obtained mass ratio, an anti-icing coating with the coverage area of ​​the topcoat on the primer controlled as needed can be obtained.

[0098] Depend on Figure 6 It can be seen that when the superhydrophobic topcoat accounts for 40%, the adhesion force of surface ice is about 76 kPa.

[0099] In the above embodiment, when the exposure area ratio of the primer and the topcoat is 50%, the surface electron microscope image is as follows: Figure 3 As shown in (a), the surface porosity is moderate and the surface contact angle is Figure 3 As shown in (b), it can reach about 150°; when the exposed area of ​​the primer and topcoat reaches 30% and 70% respectively, the mirror image of the surface is as follows Figure 4 As shown in (a), the surface porosity is low and the surface contact angle is Figure 4 As shown in (b), it can reach about 129°; when the exposure area ratios of the primer and topcoat are 60% and 40% respectively, the surface electron microscope image is as follows Figure 5 As shown in (a), the surface porosity is high and the surface contact angle is Figure 5 As shown in (b), it can reach about 159°. Figure 6As shown, when the surface is completely covered by the super-slippery surface, the ice adhesion is the lowest, about 15 kPa. Although it has the lowest ice adhesion at this time, the surface hydrophobicity is poor, and the lubricating fluid is easily lost under the long-term rain scouring, resulting in the failure of surface anti-icing. When the surface is completely covered by the super-hydrophobic topcoat, the ice adhesion after the surface is frozen is the largest, about 208 kPa. It can be seen that only when the super-slippery surface of the primer and the super-hydrophobic surface of the topcoat appear alternately, the polar ship anti-icing coating with adjustable ice adhesion proposed in the present invention can achieve both low ice adhesion and controllability adjustment of better super-hydrophobic properties.

[0100] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations on the present invention. A person skilled in the art may change, modify, replace and modify the above embodiments within the scope of the present invention without departing from the principles and intent of the present invention.

Claims

1. A polar ship anti-icing coating with adjustable ice adhesion, characterized in that: It includes a double-layer coupling structure consisting of a primer and a topcoat, wherein the coverage area of ​​the topcoat on the primer is in a dynamically controllable form; The primer has an ultra-slip surface, and its surface microstructure prevents ice crystals from embedding into the microstructure by locking lubricating oil; The topcoat is a superphobic surface obtained by directional screening and removal of magnetic particles in the topcoat coating. The micro-area distribution of the superphobic surface is complementary to the removed magnetic particles in spatial arrangement. The exposed area of ​​the supersmooth surface primer is regulated by controlling the spatial distribution of the magnetic particles.

2. The polar ship anti-icing coating with adjustable ice adhesion according to claim 1, characterized in that: The primer is an ultra-slip layer of microstructure filled with lubricating oil formed by a primer coating sprayed on the surface of a substrate, and the primer coating is a mixture of polydimethylsiloxane, dichloromethane, dimethyl silicone oil and a silane coupling agent.

3. The polar ship anti-icing coating with adjustable ice adhesion according to claim 2, characterized in that: The topcoat is a super-hydrophobic surface formed by heating the topcoat coating sprayed on the surface of the primer to cover part of the primer, so that part of the primer is exposed; the topcoat coating is composited by super-hydrophobic particles, iron powder particles wrapped by ammonium carbonate crystals, and ethanol.

4. The polar ship anti-icing coating with adjustable ice adhesion according to claim 3, characterized in that: The spraying thickness of the primer coating is 20 microns, and the spraying thickness of the topcoat coating is 10 microns.

5. The polar ship anti-icing coating with adjustable ice adhesion according to claim 3, characterized in that: Method for adjusting the coverage area of ​​the topcoat on the primer: The super-hydrophobic particles in the topcoat coating were determined to be 10-micron-sized porous silica particles; Set the exposed area ratio of the primer as needed and use the following formula to calculate the iron powder particle diameter: in, is the primer exposed area ratio, is the diameter of porous silica particles, is the diameter of iron powder particles; The mass ratio of porous silica particles to iron powder particles is calculated based on the density ratio of porous silica particles to iron powder particles, and a topcoat coating is prepared according to the obtained mass ratio, thereby obtaining an anti-icing coating with the coverage area of ​​the topcoat on the primer controlled as needed.

6. A method for preparing a polar ship anti-icing coating with adjustable ice adhesion as claimed in any one of claims 1 to 5, characterized in that The specific steps are as follows: Preparation of topcoat coating: super-hydrophobic particles, iron powder particles wrapped by ammonium carbonate crystals, and ethanol are mixed and stirred at room temperature, and then subjected to ultrasonic dispersion treatment to obtain topcoat coating; wherein the super-hydrophobic particles and the iron powder particles wrapped by ammonium carbonate crystals are used as solute particles, ethanol is used as solvent, and the mass ratio of solute particles to solvent is 2:5; Preparation of primer coating: polydimethylsiloxane, dichloromethane and dimethyl silicone oil are mixed and stirred at room temperature, and then subjected to ultrasonic dispersion treatment to obtain a coating precursor liquid, and the coating precursor liquid is mixed and stirred with a silane coupling agent to obtain a primer coating; The primer is sprayed on the surface of the substrate and dried at 60 degrees Celsius for 15 minutes to obtain a semi-cured primer; The topcoat is sprayed on the semi-cured primer surface, and then heated and cured and cooled to room temperature; during the heating process, the ammonium carbonate crystals coated on the surface of the iron powder particles volatilize, exposing the iron powder particles; The exposed iron powder particles are sucked out by an electromagnet, so that the primer at the position where the iron powder particles are located is exposed, thereby obtaining an anti-icing coating with a double layer coupling of primer and topcoat.

7. The method for preparing a polar ship anti-icing coating with adjustable ice adhesion according to claim 6, characterized in that: The specific steps of preparing the topcoat coating are as follows: The surface of porous silica particles is etched with a sodium hydroxide solution to form silica particles with nanoscale micro-surface structures; The silicon dioxide particles with nano-scale micro-surface structures are subjected to low surface energy treatment to obtain silicon dioxide nanoparticles with amphiphobic properties, i.e., superhydrophobic particles; preparing iron powder particles coated with ammonium carbonate crystals; The silicon dioxide nanoparticles with amphiphobic properties, the iron powder particles wrapped by ammonium carbonate crystals and ethanol are mixed and stirred at room temperature, and then subjected to ultrasonic dispersion treatment at room temperature to obtain a topcoat coating.

8. The method for preparing a polar ship anti-icing coating with adjustable ice adhesion according to claim 7, characterized in that: The preparation method of the iron powder particles wrapped by ammonium carbonate crystals is as follows: The iron powder particles, ammonium carbonate and water were stirred uniformly in a water bath heated at 35 degrees Celsius, and then ultrasonically dispersed to obtain a mixed solution; wherein the mass ratio of the iron powder particles, ammonium carbonate and water was 3:5:60; The mixed solution after dispersion treatment is further cooled to 15 degrees Celsius at a cooling rate of 1 degree Celsius per minute under an ultrasonic dispersion environment; The mixed solution after the cooling treatment is stirred by an electromagnet, and the particles adsorbed by the electromagnet are the iron powder particles wrapped by the ammonium carbonate crystals.

9. The method for preparing a polar ship anti-icing coating with adjustable ice adhesion according to claim 8, characterized in that: During the preparation of the primer coating, the mass ratio of polydimethylsiloxane, dichloromethane, dimethyl silicone oil and silane coupling agent is 10:20:8:

1.

10. The method for preparing a polar ship anti-icing coating with adjustable ice adhesion according to claim 9, characterized in that: The topcoat is sprayed on the semi-cured primer surface, and the heating and curing process is to increase the temperature from 95° C. to 150° C. within 30 minutes and maintain the temperature at 150° C. for 10 minutes.

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