Anti-reflection hydrophobic coating and preparation method thereof
Technical Field
The invention belongs to the technical field of materials, and particularly relates to an anti-reflection hydrophobic coating and a preparation method thereof.
Background
With the deep research make internal disorder or usurp on the super-hydrophobic structure of the bionic lotus leaf, people gradually recognize the important significance and application of the super-hydrophobic characteristic in the daily life of people. Therefore, how to construct a lotus leaf-like super-hydrophobic film through material modification and surface microstructure design has become one of the research hotspots in the field of functional materials. Many teams at home and abroad research and develop bionic lotus leaf structure hydrophobic materials, and the bionic lotus leaf structure hydrophobic materials are used on the surfaces of glass, building materials and the like, so that the super-hydrophobic materials which can achieve the hydrophobic self-cleaning effect have more and more delicate division of labor. Many groups at home and abroad do a lot of researches around the point, but most of prepared films only have the characteristic of hydrophobicity and are not generally enhanced in permeability, and most of film preparation methods are complicated and medicines are expensive to prepare.
Based on this, the team has conducted a series of studies aiming to find a more effective solution to these problems.
Disclosure of Invention
The invention provides an anti-reflection hydrophobic coating and a preparation method thereof. The anti-reflection hydrophobic coating is a silicon dioxide hydrophobic coating, and the transmittance of the anti-reflection film is higher than that of the blank glass within the light wave band range of 300-900 nm. The maximum transmittance can reach 99.539%; the water contact angle can reach more than 141 degrees.
The invention adopts the technical scheme that the anti-reflection hydrophobic coating comprises a silicon dioxide layer and a methyl-MQ silicon resin layer arranged on the silicon dioxide layer, wherein the silicon dioxide layer is prepared by adopting a sol-gel method.
Further, when the silicon dioxide layer is prepared, the raw materials are tetraethyl orthosilicate, deionized water, ethanol and ammonia water, and the volume ratio of the tetraethyl orthosilicate to the deionized water to the ethanol to the ammonia water is 4-6: 0.6-1.3: 45-51: 0.5-1.1.
Further, prior to preparation of the methyl-MQ silicone resin layer, it was mixed with tetrahydrofuran in a ratio of 0.5-1.5: 2, mixing uniformly and then using.
The invention also relates to a method for preparing the anti-reflection hydrophobic coating, which comprises the following steps:
s1, mixing tetraethyl orthosilicate, absolute ethyl alcohol, deionized water and ammonia water, magnetically stirring for 20-30 hours to obtain light blue sol, and aging for 5-15 days at room temperature to obtain silicon dioxide sol for later use;
s2, mixing the methyl-MQ silicon resin and tetrahydrofuran, and magnetically stirring for 0.5-1h at 25-30 ℃ to obtain a hydrophobic solution for later use;
s3, pulling the cleaned base material on a dip coating machine to form silica sol coated with the film S1, so that silica is attached to the base material to form a silica antireflection film, and drying;
s4, coating the hydrophobic solution in the S2 on the silicon dioxide antireflection film in the S3 in a scraping mode, and drying and annealing the treated base material to obtain the high-hydrophobicity coating.
Further, the substrate is glass, a resin material, or a metal material. Glass materials are preferred. It can also be used for aluminium sheet, fan blade, etc.
Further, before the substrate is subjected to dip coating in S3, the substrate is sequentially cleaned by detergent, ultrasonic cleaning, common water cleaning, ultrasonic cleaning, ethanol cleaning and deionized water cleaning, then dried, and finally subjected to surface treatment by a plasma machine. In the plasma treatment, the plasma power was 600w and the treatment time was 60 s.
Further, when dipping and pulling treatment are carried out in S3, the base material is dipped in the silica sol for 6-10min and then is pulled at a constant speed of 500-1500 μm/S; the thickness of the hydrophobic solution in S4 is 45-55 μm when the solution is coated by a blade.
Furthermore, the drying temperature in S3 is 100-150 ℃, and the drying time is 0.1-0.5 h.
Further, the drying temperature in S4 is 100-150 ℃, and the time is 0.2-0.6 h; and during annealing, annealing for 5-20 min at 320-450 ℃ in a muffle furnace.
The invention also relates to an application of the anti-reflection hydrophobic coating in a photovoltaic cell panel.
The methyl-MQ silicon resin is a novel organic silicon high polymer material with a three-dimensional (nonlinear) structure formed by taking Si-O bonds as a framework in molecules, and has good mechanical properties and excellent properties of high and low temperature resistance, electrical insulation, moisture resistance, water resistance and the like due to the long-chain spherical molecular structure. The structural formula is shown as follows.
The invention has the following beneficial effects:
the anti-reflection hydrophobic coating provided by the invention has a special nano-scale upper and lower layer coarse structure, has good hydrophobic and self-cleaning capabilities, and has a contact angle of 141.49 degrees; the anti-reflection effect is very good, the transmittance is higher than that of the blank glass within the light wave band range of 300-900nm, and the transmittance at 552nm reaches 99.539%.
The anti-reflection hydrophobic coating also has good durability and mechanical property and excellent uvioresistant property. The resulting samples were exposed to UVA-340 UV light for 17 hours, 4 impacts at a height of 40cm of 10g grit, and the light transmittance was still much higher than that of the clear glass after experimental testing.
The preparation method provided by the invention has the advantages of simple process and low cost, and the anti-reflection hydrophobic coating can be used on an optical device and can improve the antifouling and decontamination capabilities; the solar cell panel can be used for a photovoltaic cell panel, the visible light absorption rate of the photovoltaic panel is obviously improved, the photoelectric conversion efficiency of the photovoltaic panel is improved, and meanwhile, the solar cell panel can be effectively antifouling, dustproof and the photoelectric conversion efficiency of the solar cell is improved. The excellent uvioresistant performance of the material has great development potential in the material field, the new energy field and the environment field.
The invention adopts a two-step method, firstly uses tetraethyl orthosilicate, deionized water, absolute ethyl alcohol and ammonia water to prepare light blue sol, and then uses methyl-MQ silicon resin to carry out blade coating modification. The obtained silicon dioxide antireflection film has an antireflection value of 8.437%, and the multifunctional antireflection film with self-cleaning and high hydrophobicity is simple in preparation method and high in cost performance.
Drawings
FIG. 1 is a transmission spectrum test chart of the obtained product.
FIG. 2 shows the transmittance of the resulting product; the left side of the figure is coated and the right side is uncoated.
FIG. 3 shows the variation of water contact angle of the surface of the film with the number of sand impacts on the resulting product.
FIG. 4 shows the change in contact angle of the glass before and after the coating, wherein the left graph shows the glass before coating and the right graph shows the glass after coating.
FIG. 5 is a graph of durability of a hydrophobic antireflective film under UVA-340 ultraviolet light.
FIG. 6 is a plan SEM view of a hydrophobic antireflective film.
FIG. 7 is a graph showing a transmission spectrum test of the surface of a film in a comparative test of a silica antireflection film.
FIG. 8 is a comparison of self-cleaning of the resulting product, wherein the top is a photograph after dust flooding, the bottom is a photograph after self-cleaning, the upper product is a coated product and the lower product is an uncoated product.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention.
Example 1
Coating the small-area glass: the glass size in this example is 25 ﹡ 75 mm. The glass model is as follows: shitai pathological microscope slide.
The substrate can be written as other resin materials or metal materials, but the glass material has the best effect, and the adhesion effect between the anti-reflection hydrophobic coating and the glass is good.
Preparation of silica sol (antireflective solution): tetraethyl orthosilicate, deionized water, absolute ethyl alcohol and ammonia water are mixed in a 100ml beaker according to the volume ratio of 4.6:1.2:45:0.8, and are magnetically stirred for 25 hours at the temperature of 30 ℃ to obtain light blue sol, and the light blue sol is aged for 10 days at room temperature.
Preparation of a hydrophobic modified solvent: mixing methyl-MQ silicon resin and tetrahydrofuran according to a volume ratio of 1:2, placing the mixture in a 100ml beaker, and magnetically stirring the mixture for 0.5h at the temperature of 30 ℃ for later use;
cleaning glass: washing glass with washing powder, ultrasonic cleaning for 10min, cleaning with common water, ultrasonic cleaning with deionized water for 5min, cleaning with ethanol for 5min, and cleaning with deionized water. After drying in an oven at 60 ℃ the mixture was treated with a maximum power of 600W for 60 s.
Plasma machine 100% power treatment for 60s
Preparing a silicon dioxide antireflection film: and (3) soaking the cleaned glass for later use in silica sol (anti-reflection solution) for 10min, and then uniformly pulling the glass by using a dipping pulling film coating machine at a speed of 1200 um/s. After the silicon dioxide antireflection film is obtained, processing the silicon dioxide antireflection film in a drying oven at 110 ℃ for 0.5 h;
hydrophobic treatment of the silica sol film: and (3) coating a layer of hydrophobic modified solvent on the glass coated with the silica sol in a scraping way, placing the sample subjected to hydrophobic modification in an oven at 110 ℃ for processing for 0.5h, and annealing in a muffle furnace at 450 ℃ for 10 min. And taking out the glass after the temperature is reduced to the room temperature to obtain the high-hydrophobicity glass with the anti-reflection effect.
A UV2500 type ultraviolet-visible-near infrared spectrophotometer is used for testing the transmissivity of the silicon dioxide antireflection film, and the transmissivity of the antireflection film in the range of 300-804 nm is more than 95% in the range of 300-900nm optical band. And the maximum transmittance at 553.5nm is 99.539%, which is much higher than that of the blank glass (see figure 1), the maximum transmittance of the blank glass is 91.102%, and the anti-reflection value of the silicon dioxide anti-reflection film is 8.437%. The water contact angle of the anti-reflection film subjected to hydrophobic modification measured by a contact angle measuring instrument is 141.49 degrees, and the specific figure is shown in figure 2.
Example 2:
the glass of the anti-reflection high-hydrophobicity film prepared in the example 1 is subjected to a durability test under a UVA-340 ultraviolet lamp tube:
the prepared product is placed in a UVA-340 ultraviolet lamp tube for testing specific values of water contact angles and transmittance on the surface of the film under different irradiation times.
1. Placing the prepared product at 50cm of UVA-340 ultraviolet lamp tube in parallel;
2. the water contact angle and transmittance of the film surface at different times were measured in units of one hour.
The water contact angle and transmittance of the film surface tended to decrease with time, and the water contact angle of the film surface was 134.49 ° at 17h of irradiation. The transmittance at this time was still greater than 95%, which was much higher than 91.1% of the blank glass. Tests show that the film has excellent durability. See in particular fig. 5, where T and WCA are hydrophobic angles and transmittance as a function of exposure time.
Example 3:
application of the coating on aluminum sheets:
preparation of silica sol (antireflective solution): tetraethyl orthosilicate, deionized water, absolute ethyl alcohol and ammonia water are mixed in a 100ml beaker according to the volume ratio of 5.5:1.2:50:1, and are magnetically stirred for 25 hours at the temperature of 30 ℃ to obtain light blue sol, and the light blue sol is aged for 10 days at room temperature.
Preparation of a hydrophobic modified solvent: mixing methyl-MQ silicon resin and tetrahydrofuran according to a volume ratio of 1:2, placing the mixture in a 100ml beaker, and magnetically stirring the mixture for 0.5h at the temperature of 30 ℃ for later use;
cleaning glass: washing glass with washing powder, ultrasonic cleaning for 10min, cleaning with common water, ultrasonic cleaning with deionized water for 5min, cleaning with ethanol for 5min, and cleaning with deionized water. Drying in an oven at 60 deg.C, and treating with 600w power of a plasma machine for 60s
Preparing a silicon dioxide antireflection film: and (3) soaking the cleaned glass for later use in silica sol (anti-reflection solution) for 10min, and then uniformly pulling the glass by using a dipping pulling film coating machine at a speed of 1200 um/s. After the silicon dioxide antireflection film is obtained, processing the silicon dioxide antireflection film in a drying oven at 110 ℃ for 0.5 h;
hydrophobic treatment of the silica sol film: and (3) coating a layer of hydrophobic modified solvent on the glass coated with the silica sol in a scraping way, placing the sample subjected to hydrophobic modification in an oven at 110 ℃ for processing for 0.5h, and annealing in a muffle furnace at 450 ℃ for 10 min. And taking out the glass after the temperature is reduced to the room temperature to obtain the high-hydrophobicity glass with the anti-reflection effect. And (5) carrying out structural and morphological analysis on the product by using the SEM. See fig. 6, which shows the obvious nanometer upper and lower layer rough structure. The low surface energy of the Me-MQ silicone resin and the coarse structure formed by aggregation of the silica nanoparticles, and the air layer between the particles are the reasons for the hydrophobicity of the film.
Comparative testing of silica antireflection films:
preparation of silica sol (antireflective solution): tetraethyl orthosilicate, deionized water, absolute ethyl alcohol and ammonia water are mixed in a 100ml beaker according to the volume ratio of 3:0.4:40:1.2, and are magnetically stirred for 25 hours at the temperature of 30 ℃ to obtain light blue sol, and the light blue sol is aged for 10 days at room temperature.
Cleaning glass: washing glass with washing powder, ultrasonic cleaning for 10min, cleaning with common water, ultrasonic cleaning with deionized water for 5min, cleaning with ethanol for 5min, and cleaning with deionized water. After drying in an oven at 60 ℃, the mixture was treated with a plasma machine at 100% power for 60 seconds.
Preparing a silicon dioxide antireflection film: and (3) soaking the cleaned glass for later use in silica sol (anti-reflection solution) for 10min, and then uniformly pulling the glass by using a dipping pulling film coating machine at a speed of 1200 um/s. After the silicon dioxide antireflection film is obtained, the silicon dioxide antireflection film is treated in an oven at 110 ℃ for 0.5 h. The transmittance of the silica antireflection film was measured using a UV2500 UV-VIS-NIR spectrophotometer, and the transmittance of the control group was 87.459% maximum, as shown in FIG. 8.