CN115763580A - Self-cleaning antireflection coating on surface of transparent material and preparation method thereof - Google Patents
Self-cleaning antireflection coating on surface of transparent material and preparation method thereof Download PDFInfo
- Publication number
- CN115763580A CN115763580A CN202211429265.4A CN202211429265A CN115763580A CN 115763580 A CN115763580 A CN 115763580A CN 202211429265 A CN202211429265 A CN 202211429265A CN 115763580 A CN115763580 A CN 115763580A
- Authority
- CN
- China
- Prior art keywords
- sol
- coating
- self
- transparent material
- cleaning
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Surface Treatment Of Glass (AREA)
Abstract
The invention provides a transparent material surface self-cleaning antireflection coating and a preparation method thereof, belonging to the field of solar cells. The method mainly solves the problems of low transmittance and inconvenient cleaning of the existing substrate. The invention firstly prepares sol containing silicon dioxide hollow nano particles, then a layer of uniform titanium dioxide coating layer grows on the surface of the silicon dioxide hollow sphere, and then the titanium dioxide is converted into anatase crystal form through a unique low-temperature heat treatment mode, thereby showing more excellent self-cleaning effect. And finally, preparing a uniform coating on the surface of the transparent material in a film forming mode such as dip coating and the like, wherein the nano particles in the coating prepared by the method are uniformly distributed, the antireflection effect is obvious, the surface hydrophilicity is excellent, and the water resistance, the acid corrosion resistance and the wear resistance are excellent.
Description
Technical Field
The invention belongs to the field of solar cells, and particularly relates to a self-cleaning antireflection coating on the surface of a transparent material and a preparation method thereof.
Background
Since the 21 st century, natural disasters occur frequently in the world, and the natural disasters are inevitable for developing renewable and low-pollution novel energy sources. Solar energy is a clean and renewable energy source, the solar energy radiated to the surface of the earth each year is equivalent to 130 trillion tons of standard coal, is 1 ten thousand times of the total energy consumption of the world every year at present, and is inexhaustible.
The current solar cell generally uses photovoltaic glass to cover the surface of the component so as to protect fragile internal devices, but due to the huge difference of refractive indexes between the glass and air, incident light can be reflected on the surface of the glass, so that the average transmittance in the wave band range (380-1100 nm) of the spectral response of the crystalline silicon solar cell is only about 92%, and serious optical loss is caused. Therefore, the preparation of an antireflection film on the surface of glass to increase the transmittance of incident light has been the research target of numerous scholars all over the world.
The earliest glass antireflection films utilized acid catalyzed SiO 2 Sol as a film layer, but because of dense acid catalyzed SiO 2 The refractive index of the sol is close to 1.45, and the antireflection performance is poor, so that the acid-catalyzed SiO is often subjected to high-temperature heat treatment 2 Condensation of the sol to form fine SiO 2 And (3) nanoparticles. Because more pores are left when the particles are accumulated, the reduced refractive index of the film layer can reach a more ideal range, and the film has an excellent antireflection effect; however, due to the structure of the plurality of pore channels generated during the high-temperature heat treatment, the film layer is very easy to corrode in the natural environment, loses the antireflection effect and even influences the strength of the photovoltaic glass. In 2007, the Dismann group of the Netherlands and Sheffier, UKCooperation of Germany university develops a method for using hollow SiO 2 Antireflection coatings prepared from nanospheres using hollow SiO 2 The nanosphere has the advantage of higher porosity, and more coupling agents can be added, so that the holes are hidden in the film layer, and the nanosphere has an antireflection effect and is not easily corroded by the external environment.
However, the antireflection coating prepared by the above method does not generally have a self-cleaning effect, and the solar cell is easily contaminated by dust, sand and the like in an actual working environment, so that incident light is scattered, and the power generation efficiency is reduced. The existing solution is to regularly clean the surface of the photovoltaic glass to remove surface contamination, but the method wastes a large amount of water resources, and the used cleaning agent can pollute the environment. For this reason, a new generation of glass antireflective coatings needs to incorporate self-cleaning capabilities into the field of research.
The Chinese invention patent with the application number of 20141010758433.3 provides a preparation method of an antireflection and super-hydrophilic coating for photovoltaic glass. The method comprises the steps of preparing hollow sphere nano particles with a silicon dioxide-titanium dioxide double-layer structure, and carrying out 550 ℃ high-temperature calcination after the hollow sphere nano particles are pulled and formed into a film on a glass substrate, so that the titanium dioxide is subjected to crystal form conversion. The preparation method of the patent needs to carry out high-temperature heat treatment on the glass substrate, on one hand, a large amount of energy is consumed, on the other hand, the application range of the coating is limited, and the preparation method is not suitable for the built photovoltaic power station.
Disclosure of Invention
The invention aims to solve the problems of poor mechanical property and weather resistance and insufficient self-cleaning function of the existing antireflection coating,and are combinedThe method constructs a super-hydrophilic anti-reflection coating with good mechanical property on a transparent material substrate, does not need high-temperature heat treatment, has good universality and can be applied to various transparent surfaces such as glass, PET, PC and the like.
The invention adopts the following specific technical scheme:
in a first aspect, the invention provides a preparation method of a self-cleaning antireflection coating on the surface of a transparent material, which comprises the following specific steps:
s1: preparing initial sol containing silicon dioxide hollow nano particles by adopting a template method or a microemulsion method;
s2: adding a surfactant, a steric inhibitor and a hydrolysis inhibitor into the initial sol, and fully dissolving at room temperature to obtain a first sol; dropwise adding a titanium source compound into the first sol to obtain a second sol;
s3: carrying out primary heat treatment on the second sol, wherein the temperature of the primary heat treatment is 20-200 ℃, and the treatment time is 0.5-5 hours, so that a layer of amorphous titanium dioxide grows and coats the surface of the hollow silicon dioxide nano-particles, and then carrying out secondary heat treatment, wherein the temperature is 100-500 ℃, and the treatment time is 0.5-10 hours, so that the amorphous titanium dioxide is converted into anatase type, and the nano-particles with the silicon dioxide-titanium dioxide composite hollow structure are obtained; uniformly dispersing the composite hollow structure nano particles in water or an alcohol solvent to obtain third sol;
s4: and adding a binder into the third sol, and then coating the third sol on the surface of a transparent material by a film forming method to obtain the self-cleaning antireflection coating on the surface of the transparent material.
Preferably, the mass percent of the surfactant added in S2 is 0.1-5 wt%, the mass percent of the steric hindrance agent added is 0.05-1 wt%, and the mass percent of the hydrolysis inhibitor added is 0.01-1 wt%.
Preferably, the surfactant in S2 is a cationic surfactant.
Further, the cationic surfactant is dodecyl trimethyl ammonium chloride or hexadecyl trimethyl ammonium bromide.
Preferably, the steric inhibitor in S2 is a high molecular weight polymer.
Further, the high molecular polymer is one of hydroxypropyl cellulose, polyethylene glycol, polyethylene or polysiloxane.
Preferably, the hydrolysis inhibitor in S2 is one of acetylacetone, ethyl acetoacetate, ethylenediaminetetraacetic acid, and carboxylic acid.
Preferably, the titanium source compound in S2 is a solution prepared by mixing one or two or more of butyl titanate, methyl titanate, ethyl titanate, titanium tetraisopropoxide and titanium tetrachloride at any ratio, the mass percent of the titanium source compound is 0.1-1 wt%, and the dropping speed is 50-500 ml/l per hour.
Preferably, the alcohol solvent in S3 is a mixture of one or two or more of methanol, ethanol, propanol, isopropanol, and butanol at an arbitrary ratio.
Preferably, the binder in S4 is one or a mixture of more of silica sol, aluminum sol or titanium sol, and the added mass percentage is 0.2wt% -2 wt%.
Preferably, the film forming method in S4 is one of pulling, roll coating, dip coating, spray coating, spin coating, or spray deposition.
Preferably, the average particle diameter of the hollow silica nanoparticles prepared in S1 is 20-200 nm, and the thickness of the silica shell is 10-50 nm; and S3, the average particle size of the silicon dioxide-titanium dioxide composite hollow nano particles prepared in the step (A) is 25 to 250 nanometers, and the thickness of a titanium dioxide shell layer is 5 to 50 nanometers.
In a second aspect, the present invention provides a surface self-cleaning anti-reflective coating prepared according to the method of the first aspect.
Preferably, the thickness of the surface self-cleaning antireflection coating is 50-400 nanometers.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, a layer of titanium dioxide with controllable thickness is grown on the surface of silicon dioxide, the refractive index of the coating is reduced by utilizing the advantage of high porosity of hollow nano particles of the silicon dioxide, and the photoinduced hydrophilic characteristic of the titanium dioxide is also utilized, so that the coating has both antireflection and self-cleaning effects;
(2) The invention provides a pre-heat treatment method (namely, first heat treatment) of a titanium dioxide growth process, under the auxiliary action of various surfactants, a layer of titanium dioxide is successfully and uniformly produced on the surface of a silicon dioxide hollow nanoparticle, the agglomeration phenomenon of titanium dioxide particles is effectively inhibited, and the coating uniformity is greatly improved;
(3) The invention realizes the crystal form transformation of titanium dioxide at lower temperature, successfully transforms the titanium dioxide into anatase crystal form, avoids high-temperature heat treatment required after film formation, and can be widely applied to other non-high-temperature-resistant transparent materials (such as PET, PC and the like);
(4) In the invention, the components and concentration of the common binder are optimized, and the binding force between the silicon dioxide-titanium dioxide composite hollow nano particles and the substrate is improved, so that the coating has good mechanical properties;
(5) The surface self-cleaning antireflection coating prepared by the method has excellent antireflection effect, and the light transmittance at a wave band of 350-1200 nm is improved by 2-7%; the water drop is hydrophilic, and the water drop rapidly spreads to form a water film on the surface of the glass with the composite coating, and the contact angle is less than 20 degrees; the glass substrate with the composite coating has good friction resistance, the surface structure is hardly damaged after the surface of the glass substrate with the composite coating is rubbed back and forth for 1000 cycles by using a wet sponge, and the change degree of the transmissivity is lower than 0.5 percent.
Drawings
FIG. 1 is a transmission spectrum before and after coating of a self-cleaning antireflection coating on a glass surface prepared in example 1;
FIG. 2 is a scanning electron microscope photograph of a self-cleaning anti-reflective coating on the surface of the glass prepared in example 1;
FIG. 3 is a TEM and energy spectrum of silica-titania composite particles in the self-cleaning anti-reflective coating for glass surface prepared in example 1;
FIG. 4 is a graph of contact angle measurements for a self-cleaning anti-reflective coating on a glass surface prepared in example 1;
FIG. 5 is a comparison graph of the transmission spectra before and after rubbing of the self-cleaning anti-reflective coating on the surface of the glass prepared in example 1;
FIG. 6 is a graph showing transmission spectra before and after coating of a clean anti-reflective coating on a PET surface prepared in example 6;
fig. 7 is a contact angle measurement graph of the PET surface cleaning anti-reflective coating prepared in example 6.
Detailed Description
The invention is further illustrated and described below with reference to the drawings and the detailed description. The technical features of the embodiments of the present invention can be combined correspondingly without mutual conflict.
Example 1
The embodiment provides a preparation method of a self-cleaning antireflection coating on a glass surface, which comprises the following specific steps:
(1) The sol containing the silicon dioxide hollow nano particles is prepared by adopting a template method, which comprises the following steps: adding 0.3 g of polyacrylic acid into 6.75 ml of ammonia water, and stirring for 15 minutes to fully dissolve the polyacrylic acid and the ammonia water to obtain a polyacrylic acid-ammonia water mixed solution; dropwise adding the polyacrylic acid-ammonia water mixed solution into 120 ml of absolute ethyl alcohol, and stirring for 15 minutes to obtain a light white mixed solution; then dissolving 1 ml of tetraethoxysilane in 10 ml of absolute ethyl alcohol, slowly dropwise adding the tetraethoxysilane into the mixed solution, and stirring the mixed solution for 6 hours at room temperature after the dropwise adding is finished to obtain light blue sol containing the silicon dioxide hollow nano particles; the silica hollow nanoparticles are about 50 nanometers in size;
(2) Taking the sol containing the hollow silica nanoparticles, adding 0.5 g of hexadecyl trimethyl ammonium bromide, 0.1 g of hydroxypropyl cellulose and 0.05 ml of acetylacetone, and stirring at room temperature for 20 minutes to fully dissolve the sol to obtain a first sol; 0.2 ml of butyl titanate was mixed in a 1:10 in ethanol, and dropwise adding the mixture into the first sol at a speed of 20 ml per hour, wherein the mixture gradually turns to light yellow to obtain a second sol;
(3) Carrying out primary heat treatment on the second sol at 100 ℃ for 1 hour to obtain the amorphous titanium dioxide coated hollow silicon dioxide nano particles; carrying out secondary heat treatment on the silica hollow nano-particles coated with the amorphous titanium dioxide at 200 ℃ for 2 hours to convert the amorphous titanium dioxide into anatase type, so as to obtain silica-titanium dioxide composite hollow nano-particles; dispersing the silicon dioxide-titanium dioxide composite hollow nano particles in 60 ml of ethanol to obtain third sol;
(4) Adding 1 ml of acid-catalyzed silica sol into the third sol, and fully stirring for 30 minutes to uniformly mix the third sol and the fourth sol to obtain a fourth sol; firstly, processing a glass substrate with the size of 4cm x 4cm by acetone: ethanol: ultrasonically cleaning the glass substrate in a mixed solution with the deionized water ratio of 1; and (3) soaking the cleaned glass into the fourth sol, pulling the glass into a film at a speed of 200 mm per minute, and repeating the pulling step for 2 times to obtain a self-cleaning antireflection coating, which is marked as a coating A, on the surface of the glass substrate.
The performance test of a glass surface self-cleaning anti-reflective coating prepared in example 1:
(1) Ultraviolet visible spectrum testing
As shown in fig. 1, the maximum transmittance of the coated glass (coating a) can reach 98.5%, and compared with a blank glass (glass with no coating on the surface), the transmittance is obviously improved by more than 6% in the visible band.
(2) Scanning electron microscope test
As shown in fig. 2, the silica hollow nanoparticles in the coating a are stacked to form a loose porous film layer, so that the refractive index of the film layer is in a proper range, and the coating is uniform and flat as a whole and has no obvious agglomeration.
(3) Transmission electron microscope and energy spectrum test
As shown in FIG. 3, the coating A is subjected to a transmission electron microscope and energy spectrum test, and the structure of the coating A is clearly divided into three different shell layers, namely a hollow layer, a silicon dioxide layer and a titanium dioxide layer from inside to outside.
(4) Contact Angle testing
As shown in fig. 4, after the water drop is dropped on the coating a, the water drop rapidly spreads into a water film, the contact angle is close to 0, and the super-hydrophilic property is presented.
(5) Scrub test
After the surface of the coating A is repeatedly rubbed for 1000 cycles under the pressure of 1 thousand weights by using a wet sponge, the surface structure is not obviously damaged, and as shown in FIG. 5, the transmittance of the coating A is slightly reduced after the rubbing, but the reduction range is not more than 0.5%, which proves that the coating A has good mechanical properties.
Example 2
In this embodiment, compared to example 1, the preparation method of the self-cleaning antireflection coating on the glass surface with different polyacrylic acid dosage (polyacrylic acid dosage is 0.6 g) is specifically as follows:
(1) The sol containing the silicon dioxide hollow nano particles is prepared by adopting a template method, which comprises the following steps: adding 0.6 g of polyacrylic acid into 6.75 ml of ammonia water, and stirring for 15 minutes to fully dissolve the polyacrylic acid and the ammonia water to obtain a polyacrylic acid-ammonia water mixed solution; dropwise adding the polyacrylic acid-ammonia water mixed solution into 120 ml of absolute ethyl alcohol, and stirring for 15 minutes to obtain a light white mixed solution; then dissolving 1 ml of tetraethoxysilane in 10 ml of absolute ethyl alcohol, slowly dripping the tetraethoxysilane into the mixed solution, and stirring the mixed solution for 6 hours at room temperature after dripping is finished to obtain light blue sol containing the silicon dioxide hollow nano particles; the silica hollow nanoparticles are about 50 nanometers in size;
(2) Taking the sol containing the hollow silica nanoparticles, adding 0.5 g of hexadecyl trimethyl ammonium bromide, 0.1 g of hydroxypropyl cellulose and 0.05 ml of acetylacetone, and stirring at room temperature for 20 minutes to fully dissolve the sol to obtain a first sol; 0.2 ml of butyl titanate was mixed in a 1:10 volume ratio is dispersed in ethanol, and the mixture is dropwise added into the first sol at the speed of 20 milliliters per hour, and the mixture gradually turns to light yellow to obtain a second sol;
(3) Carrying out primary heat treatment on the second sol at 100 ℃ for 1 hour to obtain the amorphous titanium dioxide coated hollow silicon dioxide nano particles; carrying out secondary heat treatment on the silica hollow nano-particles coated with the amorphous titanium dioxide at 200 ℃ for 2 hours to convert the amorphous titanium dioxide into anatase type, so as to obtain silica-titanium dioxide composite hollow nano-particles; dispersing the silicon dioxide-titanium dioxide composite hollow nano particles in 60 ml of ethanol to obtain third sol;
(4) Adding 1 ml of acid catalytic silica sol into the third sol, and fully stirring for 30 minutes to uniformly mix the third sol and the fourth sol to obtain a fourth sol; a glass substrate with the size of 4cm x 4cm is firstly subjected to acetone: ethanol: ultrasonically cleaning the glass substrate in a mixed solution with the deionized water ratio of 1; and soaking the cleaned glass into the fourth sol, pulling the glass into a film at the speed of 200 mm per minute, and repeating the pulling step for 2 times to obtain a self-cleaning antireflection coating, which is marked as a coating B, on the surface of the glass substrate.
As shown in fig. 3, the transmission electron microscope and the energy spectrum of the coating B show that the silica hollow nanoparticles in the present embodiment have a significantly increased size and an average particle diameter of about 200 nm, compared to the silica hollow nanoparticles in the coating a. Under the condition that the rest steps are kept unchanged, the thickness of the shell layer of the silicon dioxide prepared by the method is increased, and the wave band corresponding to the highest transmittance point is red-shifted.
The effect of different amounts of titanium source compound on the self-cleaning anti-reflective coating on the surface of the prepared glass is verified by examples 3 and 4.
Example 3
This example provides a method for preparing a self-cleaning antireflection coating on a glass surface with different titanium source compound usage (butyl titanate usage is 0.1 ml) compared to example 1, specifically as follows:
(1) The sol containing the silicon dioxide hollow nano particles is prepared by adopting a template method, which comprises the following steps: adding 0.3 g of polyacrylic acid into 6.75 ml of ammonia water, and stirring for 15 minutes to fully dissolve the polyacrylic acid and the ammonia water to obtain a polyacrylic acid-ammonia water mixed solution; dropwise adding the polyacrylic acid-ammonia water mixed solution into 120 ml of absolute ethyl alcohol, and stirring for 15 minutes to obtain a light white mixed solution; then dissolving 1 ml of tetraethoxysilane in 10 ml of absolute ethyl alcohol, slowly dropwise adding the tetraethoxysilane into the mixed solution, and stirring the mixed solution for 6 hours at room temperature after the dropwise adding is finished to obtain light blue sol containing the silicon dioxide hollow nano particles; the silica hollow nanoparticles are about 50 nanometers in size;
(2) Taking the sol containing the hollow silica nanoparticles, adding 0.5 g of hexadecyl trimethyl ammonium bromide, 0.1 g of hydroxypropyl cellulose and 0.05 ml of acetylacetone, and stirring at room temperature for 20 minutes to fully dissolve the sol to obtain a first sol; 0.1 ml of butyl titanate was mixed in a 1:10 in ethanol, and dropwise adding the mixture into the first sol at a speed of 20 ml per hour, wherein the mixture gradually turns to light yellow to obtain a second sol;
(3) Carrying out primary heat treatment on the second sol at 100 ℃ for 1 hour to obtain the amorphous titanium dioxide coated hollow silicon dioxide nano particles; carrying out secondary heat treatment on the silica hollow nano-particles coated with the amorphous titanium dioxide at 200 ℃ for 2 hours to convert the amorphous titanium dioxide into anatase type, so as to obtain silica-titanium dioxide composite hollow nano-particles; dispersing the silicon dioxide-titanium dioxide composite hollow nano particles in 60 ml of ethanol to obtain third sol;
(4) Adding 1 ml of acid catalytic silica sol into the third sol, and fully stirring for 30 minutes to uniformly mix the third sol and the fourth sol to obtain a fourth sol; firstly, processing a glass substrate with the size of 4cm x 4cm by acetone: ethanol: ultrasonically cleaning the glass substrate in a mixed solution with the deionized water ratio of 1; and soaking the cleaned glass into the fourth sol, pulling the glass into a film at the speed of 200 mm per minute, and repeating the pulling step for 2 times to obtain a self-cleaning antireflection coating, which is marked as a coating C, on the surface of the glass substrate.
Compared with the coating A prepared in the example 1, the coating C has the advantages that the coating C is insufficient in generated titanium dioxide coating and poor in hydrophilic performance because the using amount of the butyl titanate is 0.1 ml and the using amount of the titanium source compound is too small, the contact angle of a coated sample is about 22.3 degrees, and the super-hydrophilic effect cannot be achieved.
Example 4
This example provides a method for preparing a self-cleaning antireflection coating on a glass surface with different titanium source compound usage (butyl titanate usage is 0.5 ml) compared to example 1, specifically as follows:
(1) The sol containing the silicon dioxide hollow nano particles is prepared by adopting a template method, which comprises the following steps: adding 0.3 g of polyacrylic acid into 6.75 ml of ammonia water, and stirring for 15 minutes to fully dissolve the polyacrylic acid and the ammonia water to obtain a polyacrylic acid-ammonia water mixed solution; dropwise adding the polyacrylic acid-ammonia water mixed solution into 120 ml of absolute ethyl alcohol, and stirring for 15 minutes to obtain a light white mixed solution; then dissolving 1 ml of tetraethoxysilane in 10 ml of absolute ethyl alcohol, slowly dripping the tetraethoxysilane into the mixed solution, and stirring the mixed solution for 6 hours at room temperature after dripping is finished to obtain light blue sol containing the silicon dioxide hollow nano particles; the silica hollow nanoparticles are about 50 nanometers in size;
(2) Taking the sol containing the hollow silica nanoparticles, adding 0.5 g of hexadecyl trimethyl ammonium bromide, 0.1 g of hydroxypropyl cellulose and 0.05 ml of acetylacetone, and stirring at room temperature for 20 minutes to fully dissolve the sol to obtain a first sol; 0.5 ml of butyl titanate was mixed in a 1:10 volume ratio is dispersed in ethanol, and the mixture is dropwise added into the first sol at the speed of 20 milliliters per hour, and the mixture gradually turns to light yellow to obtain a second sol;
(3) Carrying out primary heat treatment on the second sol at 100 ℃ for 1 hour to obtain the amorphous titanium dioxide coated silicon dioxide hollow nanoparticles; carrying out secondary heat treatment on the silica hollow nano-particles coated with the amorphous titanium dioxide at 200 ℃ for 2 hours to convert the amorphous titanium dioxide into anatase type, so as to obtain silica-titanium dioxide composite hollow nano-particles; dispersing the silicon dioxide-titanium dioxide composite hollow nano particles in 60 ml of ethanol to obtain third sol;
(4) Adding 1 ml of acid catalytic silica sol into the third sol, and fully stirring for 30 minutes to uniformly mix the third sol and the fourth sol to obtain a fourth sol; a glass substrate with the size of 4cm x 4cm is firstly subjected to acetone: ethanol: ultrasonically cleaning the glass substrate in a mixed solution with the deionized water ratio of 1; and (3) soaking the cleaned glass into the fourth sol, pulling the glass into a film at the speed of 200 mm per minute, and repeating the pulling step for 2 times to obtain a self-cleaning antireflection coating, which is marked as a coating D, on the surface of the glass substrate.
Compared with the coating C prepared in the embodiment 3, the amount of the titanium dioxide generated is gradually increased due to the increase of the amount of the titanium source compound, and the hydrophilicity is continuously enhanced. However, because the surface of titanium dioxide particles has high surface energy, the particles agglomerate with each other in order to reduce the surface energy, so that the sol cannot form a flat and uniform film layer during film coating, but form island-shaped accumulation to cause the scattering of incident light, and the transmittance at the highest point of a spectrum can only reach 93.2%.
Example 5
This example provides a method for preparing a self-cleaning anti-reflective coating on a glass surface by different heat treatments (the second heat treatment time is 4 hours) compared to example 1, which comprises the following steps:
(1) The sol containing the silicon dioxide hollow nano particles is prepared by adopting a template method, which comprises the following steps: adding 0.3 g of polyacrylic acid into 6.75 ml of ammonia water, and stirring for 15 minutes to fully dissolve the polyacrylic acid and the ammonia water to obtain a polyacrylic acid-ammonia water mixed solution; dropwise adding the polyacrylic acid-ammonia water mixed solution into 120 ml of absolute ethyl alcohol, and stirring for 15 minutes to obtain a light white mixed solution; then dissolving 1 ml of tetraethoxysilane in 10 ml of absolute ethyl alcohol, slowly dripping the tetraethoxysilane into the mixed solution, and stirring the mixed solution for 6 hours at room temperature after dripping is finished to obtain light blue sol containing the silicon dioxide hollow nano particles; the silica hollow nanoparticles are about 50 nanometers in size;
(2) Taking the sol containing the hollow silica nanoparticles, adding 0.5 g of hexadecyl trimethyl ammonium bromide, 0.1 g of hydroxypropyl cellulose and 0.05 ml of acetylacetone, and stirring at room temperature for 20 minutes to fully dissolve the sol to obtain a first sol; 0.2 ml of butyl titanate was mixed in a 1:10 in ethanol, and dropwise adding the mixture into the first sol at a speed of 20 ml per hour, wherein the mixture gradually turns to light yellow to obtain a second sol;
(3) Carrying out primary heat treatment on the second sol at 100 ℃ for 1 hour to obtain the amorphous titanium dioxide coated silicon dioxide hollow nanoparticles; carrying out secondary heat treatment on the amorphous titanium dioxide coated hollow silicon dioxide nano particles for 4 hours at 200 ℃ to convert the amorphous titanium dioxide into anatase type, thus obtaining silicon dioxide-titanium dioxide composite hollow nano particles; dispersing the silicon dioxide-titanium dioxide composite hollow nano particles in 60 ml of ethanol to obtain third sol;
(4) Adding 1 ml of acid-catalyzed silica sol into the third sol, and fully stirring for 30 minutes to uniformly mix the third sol and the fourth sol to obtain a fourth sol; firstly, processing a glass substrate with the size of 4cm x 4cm by acetone: ethanol: ultrasonically cleaning the glass substrate in a mixed solution with the deionized water ratio of 1; and (3) soaking the cleaned glass into the fourth sol, pulling the glass into a film at the speed of 200 mm per minute, and repeating the pulling step for 2 times to obtain a self-cleaning antireflection coating, which is marked as a coating E, on the surface of the glass substrate.
Compared with the coating A prepared in example 1, due to the prolonged time of the second heat treatment, the number of the titanium dioxide nanoparticles in the coating E is gradually increased, the agglomeration among the nanoparticles is caused, the sol is also easy to form island-shaped agglomeration during film coating, the scattering of incident light is caused, and the transmittance at the highest point of the spectrum can only reach 94.5%.
Example 6
The embodiment provides a method for preparing a self-cleaning antireflection coating on the surface of a transparent material by using polyethylene terephthalate (PET) as a transparent material substrate, which comprises the following specific steps:
(1) The sol containing the silicon dioxide hollow nano particles is prepared by adopting a template method, which comprises the following steps: adding 0.3 g of polyacrylic acid into 6.75 ml of ammonia water, and stirring for 15 minutes to fully dissolve the polyacrylic acid and the ammonia water to obtain a polyacrylic acid-ammonia water mixed solution; dropwise adding the polyacrylic acid-ammonia water mixed solution into 120 ml of absolute ethyl alcohol, and stirring for 15 minutes to obtain a light white mixed solution; then dissolving 1 ml of tetraethoxysilane in 10 ml of absolute ethyl alcohol, slowly dripping the tetraethoxysilane into the mixed solution, and stirring the mixed solution for 6 hours at room temperature after dripping is finished to obtain light blue sol containing the silicon dioxide hollow nano particles; the silica hollow nanoparticles have a size of about 50 nm;
(2) Taking the sol containing the hollow silica nanoparticles, adding 0.5 g of hexadecyl trimethyl ammonium bromide, 0.1 g of hydroxypropyl cellulose and 0.05 ml of acetylacetone, and stirring at room temperature for 20 minutes to fully dissolve the sol to obtain a first sol; 0.2 ml of butyl titanate was mixed in a 1:10 in ethanol, and dropwise adding the mixture into the first sol at a speed of 20 ml per hour, wherein the mixture gradually turns to light yellow to obtain a second sol;
(3) Carrying out primary heat treatment on the second sol at 100 ℃ for 1 hour to obtain the amorphous titanium dioxide coated silicon dioxide hollow nanoparticles; carrying out secondary heat treatment on the silica hollow nano-particles coated with the amorphous titanium dioxide at 200 ℃ for 2 hours to convert the amorphous titanium dioxide into anatase type, so as to obtain silica-titanium dioxide composite hollow nano-particles; dispersing the silicon dioxide-titanium dioxide composite hollow nano particles in 60 ml of ethanol to obtain third sol;
(4) Adding 1 ml of acid-catalyzed silica sol into the third sol, and fully stirring for 30 minutes to uniformly mix the third sol and the fourth sol to obtain a fourth sol; a PET substrate with the size of 4cm x 4cm is firstly subjected to acetone: ethanol: ultrasonically cleaning the PET substrate in a mixed solution with the deionized water ratio of 1; and (3) soaking the cleaned PET substrate into the fourth sol, pulling the cleaned PET substrate into a film at the speed of 200 mm per minute, and repeating the pulling step for 2 times to obtain a self-cleaning antireflection coating, which is marked as a coating F, on the surface of the PET substrate.
As shown in FIG. 6, the transmittance of coating F in the long wavelength band region was significantly improved by 7%. And (3) performing a contact angle test on the surface of the PET film after film plating, as shown in fig. 7, converting the original hydrophobic surface of the PET substrate into hydrophilic, wherein the contact angle is about 10 degrees, and the excellent super-hydrophilic characteristic of the self-cleaning anti-reflection coating on the surface is shown.
In conclusion, the sol containing the silicon dioxide hollow nano particles is prepared, then the uniform titanium dioxide coating layer grows on the surface of the silicon dioxide hollow sphere, and then the titanium dioxide is converted into the anatase crystal form through a unique low-temperature heat treatment mode, so that the self-cleaning effect is more excellent. And finally, preparing a uniform coating on the surface of the glass substrate in a dip coating mode and the like, wherein the nano particles in the coating prepared by the method are uniformly distributed, the antireflection effect is obvious, the surface hydrophilicity is excellent, and the water resistance, the acid corrosion resistance and the wear resistance are excellent.
The above-described embodiments are merely preferred embodiments of the present invention, which should not be construed as limiting the invention. Various changes and modifications may be made by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present invention. Therefore, the technical scheme obtained by adopting the mode of equivalent replacement or equivalent transformation is within the protection scope of the invention.
Claims (10)
1. A preparation method of a self-cleaning antireflection coating on the surface of a transparent material is characterized by comprising the following specific steps:
s1: preparing initial sol containing silicon dioxide hollow nano particles by adopting a template method or a microemulsion method;
s2: adding a surfactant, a spatial position resistance agent and a hydrolysis inhibitor into the initial sol, and fully dissolving at room temperature to obtain a first sol; dropwise adding a titanium source compound into the first sol to obtain a second sol;
s3: carrying out primary heat treatment on the second sol, wherein the temperature of the primary heat treatment is 20-200 ℃, and the treatment time is 0.5-5 hours, so that a layer of amorphous titanium dioxide grows and coats the surface of the hollow silicon dioxide nano particles; then, carrying out second heat treatment at 100-500 ℃ for 0.5-10 hours to convert the amorphous titanium dioxide into anatase crystal form to obtain the nano-particles with the silicon dioxide-titanium dioxide composite hollow structure; uniformly dispersing the composite hollow structure nano particles in water or an alcohol solvent to obtain third sol;
s4: and adding a binder into the third sol, and then coating the third sol on the surface of a transparent material by a film forming method to obtain the self-cleaning antireflection coating on the surface of the transparent material.
2. The method for preparing the self-cleaning antireflection coating on the surface of the transparent material as claimed in claim 1, wherein the surfactant is added in the S2 in an amount of 0.1wt% to 5wt%, the steric hindrance agent is added in an amount of 0.05wt% to 1wt%, and the hydrolysis inhibitor is added in an amount of 0.01wt% to 1wt%.
3. The method for preparing a self-cleaning anti-reflective coating on the surface of a transparent material according to claim 1, wherein the surfactant in S2 is a cationic surfactant; preferably, the cationic surfactant is dodecyl trimethyl ammonium chloride or hexadecyl trimethyl ammonium bromide.
4. The method for preparing the self-cleaning antireflection coating on the surface of the transparent material according to claim 1, wherein the steric inhibitor in S2 is a high molecular polymer; preferably, the high molecular polymer is one of hydroxypropyl cellulose, polyethylene glycol, polyethylene or polysiloxane.
5. The method for preparing a self-cleaning anti-reflective coating on the surface of a transparent material as claimed in claim 1, wherein said hydrolysis inhibitor in S2 is one of acetylacetone, ethyl acetoacetate, ethylenediaminetetraacetic acid or carboxylic acid.
6. The method for preparing a self-cleaning anti-reflective coating on the surface of a transparent material according to claim 1, wherein the titanium source compound in S2 is one or a mixture of butyl titanate, methyl titanate, ethyl titanate, titanium tetraisopropoxide and titanium tetrachloride, the mass percent of the titanium source compound is 0.1-1 wt%, and the dropping speed is 50-500 ml/l per hour.
7. The method for preparing the self-cleaning anti-reflective coating on the surface of the transparent material as claimed in claim 1, wherein the alcohol solvent in S3 is one or a mixture of methanol, ethanol, propanol, isopropanol and butanol.
8. The method for preparing the self-cleaning antireflection coating on the surface of the transparent material according to claim 1, wherein the binder in S4 is one or more of silica sol, aluminum sol or titanium sol, and the mass percentage of the binder is 0.2wt% to 2wt%; and S4, the film forming mode adopts one of lifting, roll coating, dip coating, spray coating, spin coating or atomization deposition.
9. The method for preparing the self-cleaning anti-reflection coating on the surface of the transparent material according to claim 1, wherein the average particle diameter of the hollow silica nanoparticles prepared in the step S1 is 20-200 nm, and the thickness of the silica shell is 10-50 nm; the average particle size of the silicon dioxide-titanium dioxide composite hollow nano particles prepared in the S3 is 25-250 nanometers, and the thickness of a titanium dioxide shell layer is 5-50 nanometers.
10. A transparent material surface self-cleaning anti-reflective coating prepared according to the method of any one of claims 1 to 9, wherein the thickness of the transparent material surface self-cleaning anti-reflective coating is 50 to 400 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211429265.4A CN115763580A (en) | 2022-11-15 | 2022-11-15 | Self-cleaning antireflection coating on surface of transparent material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211429265.4A CN115763580A (en) | 2022-11-15 | 2022-11-15 | Self-cleaning antireflection coating on surface of transparent material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115763580A true CN115763580A (en) | 2023-03-07 |
Family
ID=85371371
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211429265.4A Pending CN115763580A (en) | 2022-11-15 | 2022-11-15 | Self-cleaning antireflection coating on surface of transparent material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115763580A (en) |
-
2022
- 2022-11-15 CN CN202211429265.4A patent/CN115763580A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4841782B2 (en) | Low reflective film and solar panel | |
| KR101729802B1 (en) | Glass article provided with photocatalyst film | |
| CN104671672B (en) | A kind of antireflective coating liquid and preparation method thereof, photovoltaic glass and preparation method thereof, solar cell module | |
| JP2002180003A (en) | AQUEOUS COATING SOLUTION FOR ABRASION RESISTANT SiO2 ANTI- REFLECTIVE LAYER | |
| US20210324573A1 (en) | Self-cleaning coating, self-cleaning fiber, self-cleaning carpet and uses thereof | |
| Li et al. | Broadband antireflection TiO2–SiO2 stack coatings with refractive-index-grade structure and their applications to Cu (In, Ga) Se2 solar cells | |
| CN101545990A (en) | Method for forming anti-reflection coating and optical element | |
| JP2012521014A (en) | Optical coating | |
| CN105399340A (en) | Super-hydrophobic high-transmittance SiO2 anti-reflecting thin film and preparation method thereof | |
| CA2784987A1 (en) | Anti-reflective coatings and methods of making the same | |
| Xin et al. | A novel route to prepare weather resistant, durable antireflective films for solar glass | |
| US11578215B2 (en) | Coating and coating formulation | |
| Zhang et al. | Study of tri-layer antireflection coatings prepared by sol–gel method | |
| CN106082692A (en) | Self-cleaning surface structure of Nanometer dustproof and preparation method thereof | |
| Kareem et al. | Base-catalyzed synthesis of superhydrophobic and antireflective films for enhanced photoelectronic applications | |
| CN103592701B (en) | Anti-reflective coating of Fresnel lens surface and preparation method thereof | |
| CN113772961B (en) | Photovoltaic glass moth eye bionic antireflection film coating liquid and preparation method thereof, antireflection film and preparation method thereof | |
| Wu et al. | Sol–gel-derived bayberry-like SiO2@ TiO2 multifunctional antireflective coatings for enhancing photovoltaic power generation | |
| Sun et al. | Design and preparation of superhydrophobic, broadband and double-layer antireflective coatings | |
| Dong et al. | Preparation of SiO2 antireflection film with high hardness and adhesion by mPEG | |
| Xin et al. | Effects of polysiloxane doping on transmittance and durability of sol–gel derived antireflective coatings for photovoltaic glass | |
| Wu et al. | Gradient refractive index-based broadband antireflective coatings and application in silicon solar modules | |
| JPWO2016143297A1 (en) | Glass plate with coating film and method for producing the same | |
| CN110606670A (en) | Preparation method of broad-spectrum anti-reflection super-hydrophobic photovoltaic glass | |
| CN115763580A (en) | Self-cleaning antireflection coating on surface of transparent material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |