CN106752462B - Super-hydrophobic material and preparation method thereof - Google Patents

Super-hydrophobic material and preparation method thereof Download PDF

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CN106752462B
CN106752462B CN201710018781.0A CN201710018781A CN106752462B CN 106752462 B CN106752462 B CN 106752462B CN 201710018781 A CN201710018781 A CN 201710018781A CN 106752462 B CN106752462 B CN 106752462B
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superhydrophobic material
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CN106752462A (en
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陈凯
王强
夏祖西
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Second Research Institute of CAAC
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    • 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
    • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/10—Homopolymers or copolymers of unsaturated ethers
    • C—CHEMISTRY; METALLURGY
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/66—Additives characterised by particle size
    • C09D7/68—Particle size between 100-1000 nm
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/20—Acidic compositions for etching aluminium or alloys thereof
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
    • C23G5/032—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Abstract

The invention discloses a super-hydrophobic material which comprises a substrate and a coating, wherein the coating consists of the following components in parts by weight: 65-78 parts of resin and 8-16 parts of nano particles. The invention also provides a preparation method of the super-hydrophobic material. The super-hydrophobic material prepared according to the invention has the advantages of strong ultraviolet resistance, wear resistance, effective prolongation of the icing time on the surface and the like, and simultaneously prolongs the service life of the super-hydrophobic material, thus having wide market prospect.

Description

Super-hydrophobic material and preparation method thereof
Technical Field
The invention relates to a super-hydrophobic material and a preparation method thereof.
Background
Icing on the surface of the airplane has great harm to the flight safety of the airplane. Mechanical deicing, electrothermal deicing, gas-heated deicing, chemical deicing fluid deicing and other technologies are common airplane surface deicing technologies. Although the technologies solve the problem of icing on the surface of the airplane to a certain extent, the idea of deicing and ice melting is adopted, ice is removed from the surface of the airplane after being formed on the surface of the airplane, and the problems of high energy consumption, large environmental pollution and the like cannot be solved fundamentally.
The key to the icing of the aircraft surface is that the supercooled water strikes the aircraft surface and cannot be separated from the aircraft surface for a long time. The problem of icing on the surface of the airplane is solved fundamentally, and the contact time of supercooled water and the surface of the airplane needs to be shortened so that the supercooled water can fall off from the surface of the airplane before icing. Under the influence of the lotus leaf effect, researchers have proposed a super-hydrophobic surface concept. The super-hydrophobic surface is a surface with special physical and chemical properties, the contact angle of the surface is more than 150 degrees, the rolling angle is less than 10 degrees, and liquid drops which are static on the surface can quickly roll off without residue through slight disturbance, so that a method is provided for solving the icing of the surface of the airplane from the source. Tzufu et al propose a method (CN 101704410A) for preparing a nano superhydrophobic surface for aircraft anti-icing and deicing, the viscous force of water drops sliding on the surface of an aircraft body is reduced on the surface of the aircraft prepared by the method, the quantity of water drops condensed on the surface of the aircraft body is reduced, and the icing degree of the surface of the aircraft is effectively reduced.
However, a large number of studies indicate that the super-hydrophobic surface has poor durability, and after a plurality of icing and deicing cycles, the surface micro-nano structure is damaged, and the hydrophobic capability is reduced. (see S.Farhadi, M.Farzaneh, S.A.Kulinich. "Anti-iconic Performance of Superhydrophic Surface", Applied Surface Science 257(2011)6264-6269. S.A.Kulinich., S.Farhadi, K.Nose.X.W.Du "Superhydrophic Surface: ecological sensitive-repeat" Langmuir Letter 2011,27(1), 25-29). More studies have shown that superhydrophobic surfaces lose their hydrophobic ability to gradually over extended periods of exposure to ultraviolet light. Xiu, it was shown that after several hundred hours of UV light aging, superhydrophobic surfaces coated with hydrophobic coatings such as polydimethylsilane, polybutene, etc., had surface contact angles that dropped from 153 ° and 162 ° to 80 ° and 70 °, respectively, and the surfaces lost their hydrophobic properties completely. (Xiu Yonghao, the flight of surface Micro-and Nanostructures for super-hydrophobic surfaces in electronic applications, PhD distribution, Georgia Institute of Technology,2008) the aircraft flies at high altitude and is irradiated with UV light for a long time, which, if the above-mentioned problems cannot be solved, would not enable the application of super-hydrophobic surfaces on a civil aircraft. US2015/0368496a1 proposes a uv-resistant superhydrophobic coating formulation consisting of a mixture of a polyfluoro compound, silicone, zinc oxide and molybdenum disulfide. A super-hydrophobic surface prepared from the mixture at 1W/m2The contact angle of the surface is not less than 140 degrees under the irradiation of ultraviolet light for 150 hours.
Although the above invention solves the problems of poor ultraviolet resistance and poor durability of the superhydrophobic surface to a certain extent, the formulation proposed in patent US2015/0368496a1 can only ensure that the contact angle of the surface is not less than 140 ° but not 150 ° under ultraviolet light irradiation for a long time (note: when the contact angle of the surface is greater than 90 ° and less than 150 °, the surface is called a hydrophobic surface rather than a superhydrophobic surface). Further studies have found that, with the superhydrophobic surface prepared in patent US2015/0368496a1, when the ultraviolet light irradiation is intenseThe degree is improved to 2W/m2In the 150 hour aging test, the surface contact angle decreases to 120 °, and the surface hydrophobicity decreases. The superhydrophobic surface prepared according to patent US2015/0368496a1, although having a certain degree of abrasion resistance, patent case 8 shows that the superhydrophobic ability of the surface is completely lost even with an optimal formulation, by rubbing the surface for 4.5 minutes. In addition, the above formulation is mainly used for anti-hydrophobic/ice applications on cable surfaces, and when it is applied to aircraft surfaces, it is not necessarily able to simultaneously achieve multiple functions of hydrophobicity, uv resistance, abrasion resistance, etc.
Therefore, in order to overcome the defects of the existing superhydrophobic material, a new superhydrophobic material with stronger functions of hydrophobicity, ultraviolet resistance, wear resistance and the like is urgently needed to be invented, so that the problems of poor resistance and poor wear resistance of the existing superhydrophobic surface are solved.
Disclosure of Invention
In order to solve the problems, the invention provides a super-hydrophobic material which comprises a substrate and a coating, wherein the coating consists of the following components in parts by weight: 65-78 parts of resin and 8-16 parts of nano particles.
Further, the resin is composed of a silicone resin and a fluorocarbon resin; wherein the mass fraction of the organic silicon resin is 10-30%, and the preferable mass fraction is 10-22%.
Further, the organic silicon resin is selected from perfluorooctyl trimethoxy silane or perfluorooctyl triethoxy silane; the fluorocarbon resin is selected from polyvinylidene fluoride, perfluoroethyl vinyl ether or perfluoromethyl vinyl ether.
Further, the particle size of the nanoparticles is 50-500 nanometers.
Further, the nanoparticles consist of the following nanoparticles in percentage by mass:
titanium dioxide: 15-45%;
zinc oxide: 45-70%;
silica, molybdenum disulfide or activated carbon: 5-20%;
preferably, the nanoparticles consist of the following nanoparticles in percentage by mass:
titanium dioxide: 25-36%;
zinc oxide: 52-60%;
silica, molybdenum disulfide or activated carbon: 12-16%.
Further, the nanoparticles consist of the following nanoparticles in percentage by mass:
titanium dioxide with a particle size of 100-200 nm: 25%, zinc oxide with the particle size of 400-500 nm: 60%, silicon dioxide with the particle size of 400-500 nanometers: 15 percent;
or titanium dioxide with the particle size of 100-200 nanometers: 36%, zinc oxide with particle size of 100-200 nm: 52 percent, active carbon with the particle size of 400-500 nanometers: 12 percent;
or titanium dioxide with the particle size of 50-100 nanometers: 25%, zinc oxide with the particle size of 50-100 nanometers: 59 percent, molybdenum dioxide with the particle size of 300-400 nanometers: 16 percent.
Further, the substrate is a surface-passivated metal, and the preferred metal is aluminum. For example, the substrate is passivated aluminum metal or aluminum oxide metal.
In the present invention, the metallic aluminum also includes an alloy form of the metallic aluminum.
Furthermore, the surface of the substrate is provided with protrusions, and nanoparticles are attached to the surfaces of the protrusions; the projections are peak-shaped, the peak height is 20 micrometers to 60 micrometers, and the width is 20 micrometers to 100 micrometers. I.e. the surface is a micro-nano micro-structure.
Further, the protrusions are prepared by an etching method, and the etching is performed in hydrofluoric acid or hydrochloric acid.
The invention also provides a method for preparing the super-hydrophobic material, which comprises the following steps:
(1) taking a substrate material and etching;
(2) coating a coating and drying to obtain the coating.
A more specific embodiment is as follows:
before etching, the metal aluminum sheet or metal aluminum oxide is cleaned by organic reagents such as ethanol, acetone, toluene, isopropanol and the like. The etching is carried out in hydrofluoric acid with the molar concentration of 2-5mol/L, the etching time is not more than 3 minutes each time, and the process is repeated for at least 5 times. More preferably, the etching is carried out in hydrofluoric acid with a molar concentration of 2.5mol/L, each etching is carried out for 3 minutes, and the process is repeated for 5 times. The etching can also be carried out in hydrochloric acid with a molar concentration of 3-5mol/L, wherein each etching time is not more than 5 minutes, and the process is repeated at least 5 times. More preferably, the etching is carried out in hydrochloric acid with a molar concentration of 3mol/L, each etching is carried out for 4 minutes, and the process is repeated for 5 times. In order to ensure the uniformity of etching, when the metal aluminum plate or the metal aluminum oxide is completely immersed in the etching solution, the metal aluminum plate or the metal aluminum oxide uniformly rotates in the etching solution at the maximum rotating speed of not more than 20 r/min. Preferably, the rotating speed of the metal plate in the etching solution is 10 r/min. The surface after etching has protrusions in the shape of peaks, the height of the peaks is 20-60 micrometers, and the width of the peaks is 20-100 micrometers. I.e. a hydrophobic microstructured surface is formed.
And then coating the super-hydrophobic coating containing the multi-component nano particles on the surface of the hydrophobic microstructure, placing the surface in an anaerobic environment, and drying for at least 1 hour in an environment of 90-150 ℃. And then placing the mixture in an anaerobic environment, and drying the mixture for at least 1 hour in an environment of 160-250 ℃.
The super-hydrophobic material prepared by the technology has the advantages of strong ultraviolet resistance, wear resistance, effective prolongation of the icing time on the surface and the like. The surface contact angle is more than 150 degrees, and the contact angle lag is less than 10 degrees. The strength is 2W/m after 150 hours2The contact angle of the surface is reduced to less than 10 degrees under the irradiation of ultraviolet light, and the ultraviolet resistance of the surface is obviously enhanced. In addition, the super-hydrophobic material prepared according to the invention can prolong the time of icing water drops on the surface by more than 250s, and the surface contact angle is reduced by no more than 10 degrees after 30 deicing and icing cycles.
Compared with the prior art, the invention has the advantages that:
(1) the invention simultaneously realizes the functions of hydrophobicity, ultraviolet resistance, wear resistance and the like of the super-hydrophobic surface.
(2) The problem of poor durability of the super-hydrophobic material is solved, and the service life of the super-hydrophobic material is prolonged.
Therefore, the super-hydrophobic material prepared by the method has the advantages of strong ultraviolet resistance, wear resistance, effective prolongation of the icing time on the surface and the like, and simultaneously prolongs the service life of the super-hydrophobic material, thereby having wide market prospect.
Obviously, many modifications, substitutions, and variations are possible in light of the above teachings of the invention, without departing from the basic technical spirit of the invention, as defined by the following claims.
The present invention will be described in further detail with reference to the following examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
Drawings
FIG. 1 is a scanning electron micrograph of the superhydrophobic surface in example 1.
Detailed Description
The raw materials and equipment used in the embodiment of the present invention are known products and obtained by purchasing commercially available products.
The metal surface profile was observed using a scanning electron microscope.
Surface contact angle and contact angle hysteresis can be measured using a contact angle meter.
The method for measuring the icing time of the water drops on the surface is as follows: and (3) placing the solid surface in an environment box at the temperature of-10 ℃, placing 0.05mL of liquid drop on the super-hydrophobic surface, starting timing and carrying out real-time observation, wherein the time required by the water drop to be completely frozen is the time for the water drop to be frozen on the surface in the environment at the temperature of-10 ℃.
The first icing and deicing cycle is that 0.05mL of liquid drops are changed from a transparent state to an opaque state on a super-hydrophobic surface in an environment at the temperature of-10 ℃, ice particles are removed from the surface by a shovel at the same temperature after the liquid drops are completely iced, and then the surface is placed in a 30 ℃ thermostat to remove residual moisture on the surface.
Example 1
The metal aluminum alloy is taken as a substrate, is polished for at least 5 times by using 360-mesh sand paper and is then placed in an ultrasonic water bath for cleaning. Thereafter, it was washed with isopropyl alcohol. After the above operation was completed, it was etched in 2.5mol/L hydrofluoric acid for 3 minutes. In the process, the aluminum plate rotates uniformly in the etching solution at a speed of 16 r/min. The above operation was repeated 5 times. Thereafter, the metallic aluminum alloy was vertically immersed into the hydrophobic coating layer containing the nanoparticles at a speed of 0.1 mm/s. And after the aluminum sheet is completely immersed, rotating the aluminum sheet at the speed of 10r/min, wherein the immersion time is not less than 7 minutes. The operation was repeated at least 5 times. The coating is formed by mixing organic resin, an organic solvent and nano particles, wherein the mass fraction of the organic resin is 65%, the mass fraction of the organic solvent is 19%, and the mass fraction of the nano particles is 16%. Wherein the organic resin is a mixture of perfluoroethyl vinyl ether (CAS No.10493-43-3) and perfluorooctyl triethoxysilane (CAS:51851-37-7), the mass fraction of the perfluoroethyl vinyl ether in the organic resin is 78%, and the mass fraction of the perfluorooctyl triethoxysilane is 22%. The organic solvent is petroleum ether. The nano particles are a mixture of 100-200 nm titanium dioxide, 400-500 nm zinc oxide and 400-500 nm silicon dioxide, and the mass fractions of the nano particles are respectively 25%, 60% and 15%. After the impregnation was completed, the mixture was placed in a nitrogen atmosphere, dried in an oven at 120 ℃ for 1.5 hours, and then dried in an oven at 200 ℃ for 1 hour.
The super-hydrophobic surface prepared by the method has irregular bulges, the bulges are in a peak shape, the height of the peak is 20 micrometers to 60 micrometers, and the width of the peak is 20 micrometers to 100 micrometers, as shown in figure 1. The surface contact angle of the surface was 158.1 deg., the contact angle hysteresis was 7.2 deg.. The icing delay of water drops on the surface in the environment of-10 ℃ is 272 s. At 2W/m2After the ultraviolet irradiation is carried out for 150 hours, the surface contact angle is 151.2 degrees, the contact angle is delayed by 8.7 degrees, and the icing is delayed for 261s in an environment with the temperature of minus 10 ℃. At 2W/m2After the ultraviolet light is irradiated for 300 hours, the contact angle of the surface is 145.8 degrees, the contact angle is lagged by 12.7 degrees, the icing is delayed by 234s in the environment of-10 ℃, and the ultraviolet resistance of the surface is obviously increased. After 10 icing and deicing cycles, the super-hydrophobic surface prepared by the method has a surface contact angle of 153.7 degrees, a contact angle lag of 9.1 degrees and an icing delay of 262s in an environment at-10 ℃. After 30 icing and deicing cycles, the surface contact angle is 150.1 degrees, the contact angle is delayed by 10.3 degrees and the temperature is-10 DEG CIn the environment, icing of the surface is delayed 248 s.
Example 2
And (3) polishing the super-hydrophobic surface I, which is a substrate made of metal aluminum alloy for at least 5 times by using 360-mesh abrasive paper, and then cleaning the super-hydrophobic surface I in an ultrasonic water bath. Thereafter, it was washed with toluene. After the above operation was completed, it was etched in 3mol/L hydrochloric acid for 4 minutes, and the above operation was repeated 5 times. Thereafter, the metallic aluminum alloy was dipped into the hydrophobic coating layer containing the nanoparticles at a speed of 0.1 mm/s. And after the aluminum sheet is completely immersed, rotating the aluminum sheet at the speed of 10r/min, wherein the immersion time is not less than 5 minutes. The above operation was repeated 5 times. The coating is formed by mixing organic resin, an organic solvent and nano particles, wherein the mass fraction of the organic resin is 78%, the mass fraction of the organic solvent is 12%, and the mass fraction of the nano particles is 10%. Wherein the organic resin is a mixture of perfluoromethyl vinyl ether (CAS No.1187-93-5) and perfluorooctyl trimethoxy silane (CAS No: 85857-16-5), the mass fraction of the perfluoromethyl vinyl ether in the organic resin is 84%, and the mass fraction of the perfluorooctyl trimethoxy silane in the organic resin is 16%. The organic solvent is petroleum ether. The nano particles are a mixture of titanium dioxide with the particle size of 100-200 nm, zinc oxide with the particle size of 100-200 nm and activated carbon with the particle size of 400-500 nm, and the mass fractions of the titanium dioxide, the zinc oxide with the particle size of 100-200 nm and the activated carbon with the particle size of 400-500 nm are respectively 36%, 52% and 12%. After the impregnation is completed, the mixture is placed in a nitrogen environment, dried in an oven at 90 ℃ for 1 hour, and then dried in an environment at 180 ℃ for 2 hours. The prepared super-hydrophobic surface has irregular protrusions which are in a peak shape, the height of the peak is 20 micrometers to 50 micrometers, and the width of the peak is 30 micrometers to 100 micrometers.
For comparison, a superhydrophobic surface II was prepared. After the hydrophobic structure is successfully prepared on the surface of the metal aluminum alloy, the metal aluminum alloy is immersed into the hydrophobic coating at the speed of 0.1 mm/s. The coating is formed by mixing organic resin, an organic solvent and nano particles, wherein the mass fraction of the organic resin is 78%, the mass fraction of the organic solvent is 12%, and the mass fraction of the nano particles is 10%. Wherein the organic resin is perfluorooctyl trimethoxy silane, the organic solvent is petroleum ether, and the nanoparticles are a mixture of titanium dioxide with the particle size of 100-200 nm and zinc oxide with the particle size of 100-200 nm, and the mass fractions of the titanium dioxide and the zinc oxide are respectively 36% and 64%.
For comparison, a superhydrophobic surface III was prepared, and after the metal aluminum alloy surface successfully prepared a hydrophobic structure, it was immersed in a hydrophobic coating at a speed of 0.1 mm/s. The coating is formed by mixing organic resin, an organic solvent and nano particles, wherein the mass fraction of the organic resin is 78%, the mass fraction of the organic solvent is 12%, and the mass fraction of the nano particles is 10%. Wherein the organic resin is a mixture of perfluoromethyl vinyl ether (CAS No.1187-93-5) and perfluorooctyl trimethoxy silane (CAS No: 85857-16-5), the mass fraction of the perfluoromethyl vinyl ether in the organic resin is 84%, and the mass fraction of the perfluorooctyl trimethoxy silane in the organic resin is 16%. The organic solvent is petroleum ether. The nano-particles are zinc oxide with the particle size of 100-200 nm.
The results of the performance tests on the three superhydrophobic surfaces are shown in table 1.
TABLE 1 Performance test results for three superhydrophobic surfaces of this example
Figure BDA0001207587960000071
Example 3
And (3) polishing the super-hydrophobic surface I, which is a substrate made of metal aluminum alloy for at least 5 times by using 360-mesh abrasive paper, and then cleaning the super-hydrophobic surface I in an ultrasonic water bath. Thereafter, it was washed with isopropyl alcohol. After the above operation was completed, it was etched in 3mol/L hydrochloric acid for 4 minutes, and the above operation was repeated 5 times. Thereafter, the metallic aluminum alloy was vertically immersed into the hydrophobic coating layer containing the nanoparticles at a speed of 0.1 mm/s. And after the aluminum sheet is completely immersed, rotating the aluminum sheet at the speed of 10r/min, wherein the immersion time is not less than 5 minutes. The above operation was repeated at least 5 times. The coating is formed by mixing organic resin, an organic solvent and nano particles, wherein the mass fraction of the organic resin is 78%, the mass fraction of the organic solvent is 14%, and the mass fraction of the nano particles is 8%. Wherein the organic resin is a mixture of perfluoroethyl vinyl ether (CAS No.10493-43-3) and perfluorooctyl trimethoxysilane (CAS No: 85857-16-5), the mass fraction of the perfluoroethyl vinyl ether in the organic resin is 90%, and the mass fraction of the perfluorooctyl trimethoxysilane is 10%. The organic solvent is petroleum ether. The nano particles are a mixture of titanium dioxide with the particle size of 50-100 nanometers, zinc oxide with the particle size of 50-100 nanometers and molybdenum dioxide with the particle size of 300-400 nanometers, and the mass fractions of the titanium dioxide, the zinc oxide and the molybdenum dioxide are respectively 25%, 59% and 16%. After the impregnation was completed, it was placed in a nitrogen atmosphere, dried in an oven at 120 ℃ for 1.5 hours, and further dried at 200 ℃ for 1 hour. The prepared super-hydrophobic surface has irregular protrusions which are in a peak shape, the height of the peak is 25 micrometers to 50 micrometers, and the width of the peak is 25 micrometers to 90 micrometers. .
Superhydrophobic surface II, prepared according to patent US2015/0368496a 1.
Superhydrophobic surface III, prepared according to chinese patent CN 101704410 a.
The results of the performance tests on the three superhydrophobic surfaces are shown in table 1.
Table 2 results of performance tests of three superhydrophobic surfaces of this example
Figure BDA0001207587960000081
In conclusion, the super-hydrophobic material has the advantages of strong ultraviolet resistance, wear resistance, capability of effectively prolonging the icing time on the surface and the like, and has wide market prospect.
Wherein, the wear resistance is characterized by whether the surface has super-hydrophobic performance after multiple icing and deicing cycles. After the surface has been frozen, the ice is removed from the surface by mechanical deicing, as described in the specific embodiments. For example, a small shovel, or sandpaper or the like is used. As shown in example 1, the surface contact angle before deicing was 158.1 ° and the contact angle hysteresis was 7.2 °, and after 30 cycles of deicing with ice, the surface contact angle was 150.1 °, the contact angle hysteresis was 10.3 °, and the surface contact angle was 150 ° or more. For the surface which is not wear-resistant, the mechanical deicing method is used for deicing the surface, and after 30 icing and deicing cycles, the surface contact angle is mostly reduced to below 130 degrees.

Claims (10)

1. A superhydrophobic material, comprising: the coating comprises a substrate and a coating, wherein the coating consists of the following components in parts by weight: 65-78 parts of resin and 8-16 parts of nano particles; the nano particles consist of the following nano particles in percentage by mass:
titanium dioxide with a particle size of 100-200 nm: 25%, zinc oxide with the particle size of 400-500 nm: 60%, silicon dioxide with the particle size of 400-500 nanometers: 15 percent;
or titanium dioxide with the particle size of 100-200 nanometers: 36%, zinc oxide with particle size of 100-200 nm: 52 percent, active carbon with the particle size of 400-500 nanometers: 12 percent;
or titanium dioxide with the particle size of 50-100 nanometers: 25%, zinc oxide with the particle size of 50-100 nanometers: 59 percent, molybdenum dioxide with the particle size of 300-400 nanometers: 16 percent.
2. The superhydrophobic material of claim 1, wherein: the resin consists of organic silicon resin and fluorocarbon resin; wherein the mass fraction of the organic silicon resin is 10-30%.
3. The superhydrophobic material of claim 2, wherein: the mass fraction of the organic silicon resin is 10-22%.
4. The superhydrophobic material of claim 2, wherein: the organic silicon resin is selected from perfluorooctyl trimethoxy silane or perfluorooctyl triethoxy silane; the fluorocarbon resin is selected from polyvinylidene fluoride, perfluoroethyl vinyl ether or perfluoromethyl vinyl ether.
5. The superhydrophobic material of claim 1, wherein: the substrate is a metal with a passivated surface.
6. The superhydrophobic material of claim 5, wherein: the surface-passivated metal is aluminum.
7. The superhydrophobic material of claim 1, wherein: the surface of the substrate is provided with a bulge, and nanoparticles are attached to the surface of the bulge; the projections are peak-shaped, have a height of 20 to 60 microns and a width of 20 to 100 microns.
8. The superhydrophobic material of claim 7, wherein: the bumps are prepared by etching in concentrated acid.
9. The superhydrophobic material of claim 8, wherein: the concentrated acid is hydrofluoric acid or hydrochloric acid.
10. A method of preparing a superhydrophobic material according to any of claims 1-9, wherein: the method comprises the following steps:
(1) taking a substrate material and etching;
(2) coating a coating and drying to obtain the coating.
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