CN116621465A - Wear-resistant hydrophobic self-cleaning anti-reflection coating and preparation method thereof - Google Patents

Wear-resistant hydrophobic self-cleaning anti-reflection coating and preparation method thereof Download PDF

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CN116621465A
CN116621465A CN202310548375.0A CN202310548375A CN116621465A CN 116621465 A CN116621465 A CN 116621465A CN 202310548375 A CN202310548375 A CN 202310548375A CN 116621465 A CN116621465 A CN 116621465A
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sol
wear
coating
hydrophobic self
reflection coating
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陈若愚
董謦
贾倩
王红宁
刘小华
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Changzhou University
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/001—General methods for coating; Devices therefor
    • C03C17/002—General methods for coating; Devices therefor for flat glass, e.g. float glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/25—Oxides by deposition from the liquid phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
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    • C03C2217/213—SiO2
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/73—Anti-reflective coatings with specific characteristics
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/78—Coatings specially designed to be durable, e.g. scratch-resistant
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/111—Deposition methods from solutions or suspensions by dipping, immersion
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Abstract

The invention belongs to the technical field of coatings, and particularly relates to a wear-resistant hydrophobic self-cleaning anti-reflection coating and a preparation method thereof. Tetraethyl orthosilicate and fluorine-containing silane are used as silicon sources, an acidic fluorine-silicon sol is synthesized by a sol-gel method under an acidic condition, tetraethyl orthosilicate is used as the silicon sources, and 50nmSiO is synthesized under an alkaline condition 2 And (3) mixing the small ball sol with acid fluorosilicone sol after ammonia removal, plating a layer of mixed fluorosilicone sol coating on a high borosilicate glass substrate by using a dipping-pulling method, and finally curing the mixed fluorosilicone sol coating in an oven at 200 ℃ for 1h to obtain the wear-resistant hydrophobic self-cleaning anti-reflection coating. The average light transmittance of the coating prepared by the invention can reach 95.57 percent in the visible light range, the water contact angle is 127 degrees, the hardness is 7H, after 1000 times of alcohol cotton ball friction, the light transmittance of the coating does not change obviously, and the hydrophobic self-cleaning anti-reflection coating has high wear resistance, firmness and self-cleaning performance.

Description

Wear-resistant hydrophobic self-cleaning anti-reflection coating and preparation method thereof
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a wear-resistant hydrophobic self-cleaning anti-reflection coating and a preparation method thereof.
Background
In the past twenty years, the use of photovoltaic methods to convert solar energy into electrical energy has become more and more common worldwide, and photovoltaic energy systems generate electricity according to the amount of sunlight reaching solar cells, but since solar panels are used in outdoor environments for a long time, the reflection effect of the surfaces of the solar panels and the influence of dust, dirt and other factors in the external environments on the solar energy reaching the solar cells can be reduced, and finally the output power is reduced, so that in order to overcome the problems, the preparation of a coating with excellent hydrophobic self-cleaning performance, antireflection performance and mechanical performance has important significance.
Methods for preparing the hydrophobic self-cleaning anti-reflection coating are various, such as a template method, a Chemical Vapor Deposition (CVD) method, a spray method, a sol-gel method, and the like. The sol-gel method is a superior method compared with other methods because of low process temperature, low cost, high purity, and the ability to deposit thin films on substrates of different shapes and sizes. However, the hydrophobic self-cleaning anti-reflection coating prepared by the sol-gel method has poor mechanical properties, namely poor adhesive force with a substrate and poor wear resistance, and is limited in outdoor large-scale application, so that the preparation of the hydrophobic self-cleaning anti-reflection coating with stable mechanical properties has important significance in practical application, and the improvement of the mechanical stability of the hydrophobic self-cleaning anti-reflection coating is a great challenge.
Minzhen Zhong prepared hydrophobic SiO using TEOS and Methyltriethoxysilane (MTES) as precursors 2 The nano particles are dispersed in ethanol, and the epoxy resin is used as a bonding layer to prepare the two-layer epoxy/silicon dioxide transparent super-hydrophobic coating with excellent mechanical properties. Although the method realizes the mechanical stability and the hydrophobic self-cleaning performance of the coating, the light transmission performance of the coating is obviously reduced, and the anti-reflection effect of the coating cannot be realized. Thus, it is a challenging task to produce a coating that combines hydrophobic self-cleaning properties, anti-reflective properties, and mechanical properties.
Disclosure of Invention
In order to solve the technical problems pointed out in the background art, the invention provides a wear-resistant hydrophobic self-cleaning anti-reflection coating and a preparation method thereof: acidic fluorosilicone sol and silica solid sphere sol are prepared by a sol-gel method, and ammonia is removed from the silica solid sphere solThen, the two are mixed according to SiO in the solid silica ball sol and the acidic fluorosilicone sol 2 Mixing the above materials at different molar ratios, aging, combining acidic fluorosilicone sol and silica solid sphere sol, wrapping and filling the mixture in the middle of silica solid sphere nano particles, then adopting a dipping-pulling method to simultaneously plate a single-layer coating on two sides of glass, and curing in an oven to obtain the wear-resistant hydrophobic self-cleaning anti-reflection coating.
The preparation method mainly comprises the following steps:
(1) Absolute ethyl alcohol (EtOH) is used as a solvent, concentrated hydrochloric acid (HCl) is used as a catalyst, tetraethyl orthosilicate (TEOS) and fluorine-containing silane are used as silicon sources, a sol-gel method is adopted to prepare acidic fluorosilicone sol by vigorously stirring in a water bath kettle at 30 ℃ for 120min, and the acidic fluorosilicone sol is aged;
wherein Si is Total (S) (TEOS/FAS-9): etOH: the molar ratio of HCl is 1:33-34:0.63-0.65, the molar ratio of tetraethyl orthosilicate (TEOS) to the fluorine-containing silane is 8-10:1-2, wherein the aging time is 5 days;
the fluorine-containing silane is nonafluorohexyl triethoxysilane (FAS-9) or perfluorodecyl triethoxysilane (FAS-17).
Absolute ethyl alcohol (EtOH) is used as solvent, ammonia (NH) 4 OH) as a catalyst, tetraethyl orthosilicate (TEOS) as a silicon source, and preparing SiO by vigorously stirring for 20min at 25 ℃ by adopting a sol-gel method and aging for 2 days 2 Solid pellet sol, siO 2 Placing the solid ball sol in a fume hood, vigorously stirring to remove ammonia, and supplementing solvent after ammonia removal until the mass is equal to that before ammonia removal;
when TEOS: etOH: NH (NH) 4 The molar ratio of OH is 1-2:38:0.27-1.8, and the particle size of the prepared silica solid sphere sol is 20-100nm.
(2) By mixing solid sphere sol of silicon dioxide with acidic fluorosilicone sol according to SiO 2 Mixing the mixture in different molar ratios to obtain uniform and stable mixed sol;
wherein, siO in the solid silica ball sol and the acidic fluorosilicone sol 2 The molar ratio of (2) is 9:1-6:4.
(3) The mixed sol is plated on a glass substrate by adopting a dipping and pulling method, and then the glass substrate is put into a baking oven at 200 ℃ for curing for 1h.
The lifting speed of the dipping lifting is 1000-1500 mu m/s, and the dipping time is 360s.
Compared with the prior art, the invention has the advantages that:
1. the preparation method has the advantages that the sol-gel method is adopted to prepare the acidic fluorosilicone sol and the silica solid ball sol, the preparation process is simple and easy to apply, and the sol-gel method does not need expensive equipment or high-temperature treatment and can also prepare the coating with high performance and low cost.
2. TEOS and fluorine-containing silane are used as silicon sources of the acidic fluorosilicon sol, and fluorine-containing groups in the fluorine-containing silane can reduce the surface energy of the coating, so that a foundation is laid for the hydrophobic property of the coating.
3. Solid silica ball sol and acid fluorosilicone sol are mixed according to SiO 2 The spherical nano particles of the silica solid sphere provide roughness for the coating, a certain roughness is needed by the hydrophobic coating, because a large number of hydroxyl groups exist on the surface of the silica solid spherical nano particles, fluorine-containing side chain groups in the acidic fluorosilicon sol can replace more hydroxyl groups on the surface of the silica solid spherical nano particles, the particle size is enlarged, when the fluorine-containing acid sol is increased to a certain concentration, the linear chain fluorine-containing acid sol is filled between the silica solid spherical nano particles, the mechanical property of the coating can be improved, and the wear resistance of the coating is improved.
4. The dipping-pulling method is adopted to plate a single-layer coating on two sides of the glass substrate, the surface of the plated coating is smooth and uniform, and experimental results show that the average light transmittance of the coating can reach 95.57 percent, and the coating has the anti-reflection performance.
5. The coating prepared by the process has the advantages of having both hydrophobic property, antireflection property and wear resistance, having average light transmittance up to 95.57 percent, water contact angle of 127 degrees, hardness up to 7H, cleaning dirt on the surface of the coating, and good self-cleaning effect, and has great development prospect in the application of semiconductor devices, optical sensors and solar photovoltaic panels.
Description of the drawings:
FIG. 1 is a transmission electron microscope image of 50nm silica nanoparticles obtained in example 3 of the present invention.
FIG. 2 is a cross-sectional view of a scanning electron microscope of the coating obtained in example 3 of the present invention.
FIG. 3 is a photograph of the coating obtained in example 3 of the present invention as observed by a microscope after hardness test.
FIG. 4 is a self-cleaning photograph of the coating obtained in example 3 of the present invention.
Detailed Description
The invention is further described below in connection with examples, but is not limited thereto.
Example 1
(1) Absolute ethyl alcohol (EtOH) is used as a solvent, concentrated hydrochloric acid (HCl) is used as a catalyst, tetraethyl orthosilicate (TEOS) and nonafluorohexyl triethoxysilane (FAS-9) are used as silicon sources, an acidic fluorosilicone sol is prepared by a sol-gel method, and aging is carried out;
wherein Si is Total (S) (TEOS/FAS-9): etOH: the molar ratio of HCl is 1:33:0.63, tetraethyl orthosilicate (TEOS) and nonafluorohexyltriethoxysilane (FAS-9) in a molar ratio of 10:1, aging for 5 days;
absolute ethyl alcohol (EtOH) is used as solvent, ammonia (NH) 4 OH) as a catalyst, tetraethyl orthosilicate (TEOS) as a silicon source, and adopting a sol-gel method to prepare 50nm SiO 2 Solid pellet sol, siO 2 Placing the solid ball sol in a fume hood, vigorously stirring to remove ammonia, and supplementing solvent after ammonia removal until the mass is equal to that before ammonia removal;
wherein, TEOS: etOH: NH (NH) 4 The molar ratio of OH is 1:38:0.46.
(2) SiO of 50nm 2 Solid ball sol and acid fluorosilicone sol are prepared according to SiO 2 Molar ratio 9:1, and aging for 2 days to obtain uniform and stable mixed sol.
(3) Coating is plated by adopting a dipping-pulling method, the pulling speed is 1000 mu m/s, the dipping time is 360s, and then the coating is placed in a baking oven at 200 ℃ for curing for 1h, so that the wear-resistant hydrophobic self-cleaning anti-reflection coating is prepared. The average light transmittance of the coating in the visible light range can reach 96.05%, the water contact angle is 118 degrees, the hysteresis angle is 15 degrees, the hardness is 4H, and the average light transmittance is 92.05% after the alcohol cotton ball is rubbed 1000 times.
Example 2
Acidic fluorosilicon sol and SiO 2 The solid sphere sol was prepared as in example 1.
(1) SiO of 50nm 2 Solid ball sol and acid fluorosilicone sol are prepared according to SiO 2 Molar ratio 8:2, mixing and aging for 2 days to obtain uniform and stable mixed sol.
(2) Coating is plated by adopting a dipping-pulling method, the pulling speed is 1000 mu m/s, the dipping time is 360s, and then the coating is placed in a baking oven at 200 ℃ for curing for 1h, so that the wear-resistant hydrophobic self-cleaning anti-reflection coating is prepared. The average light transmittance of the coating in the visible light range can reach 95.72%, the water contact angle is 124 degrees, the hysteresis angle is 8 degrees, the hardness is 6H, and the average light transmittance is 94.13% after the alcohol cotton ball is rubbed 1000 times.
Example 3
Acidic fluorosilicon sol and SiO 2 The solid sphere sol was prepared as in example 1.
(1) SiO of 50nm 2 Solid ball sol and acid fluorosilicone sol are prepared according to SiO 2 Molar ratio 7:3 mixing and aging for 2 days to obtain uniform and stable mixed sol.
(2) Coating is plated by adopting a dipping-pulling method, the pulling speed is 1000 mu m/s, the dipping time is 360s, and then the coating is placed in a baking oven at 200 ℃ for curing for 1h, so that the wear-resistant hydrophobic self-cleaning anti-reflection coating is prepared. The average light transmittance of the coating in the visible light range can reach 95.57%, the water contact angle is 127%, the hysteresis angle is 4%, the hardness is 7H, and the average light transmittance of the alcohol cotton ball after 1000 times of friction is 95.18%.
The left graph of fig. 3 shows that the coating hardness can reach 7H without the occurrence of scratches using a pencil with a hardness of 7H, and the right graph shows that the coating hardness does not reach 8H with the occurrence of scratches using a pencil with a hardness of 8H.
Example 4
Acidic fluorosilicon sol and SiO 2 The solid sphere sol was prepared as in example 1.
(1) SiO of 50nm 2 Solid ball sol and acid fluorosilicone sol are prepared according to SiO 2 Molar ratio 6:4, mixing and aging for 2 days to obtain uniform and stable mixed sol.
(2) Coating is plated by adopting a dipping-pulling method, the pulling speed is 1000 mu m/s, the dipping time is 360s, and then the coating is placed in a baking oven at 200 ℃ for curing for 1h, so that the wear-resistant hydrophobic self-cleaning anti-reflection coating is prepared. The average light transmittance of the coating in the visible light range can reach 94.50%, the water contact angle is 116 degrees, the hysteresis angle is 15 degrees, the hardness is 7H, and the average light transmittance is 94.16% after the alcohol cotton ball is rubbed 1000 times.
Example 5
(1) Absolute ethyl alcohol (EtOH) is used as a solvent, concentrated hydrochloric acid (HCl) is used as a catalyst, tetraethyl orthosilicate (TEOS) and nonafluorohexyl triethoxysilane (FAS-9) are used as silicon sources, an acidic fluorosilicone sol is prepared by a sol-gel method, and aging is carried out;
wherein Si is Total (S) (TEOS/FAS-9): etOH: the molar ratio of HCl is 1:34:0.65, tetraethyl orthosilicate (TEOS) and fluorosilane in a molar ratio of 8:2, and aging time of 5 days;
(2) SiO of 50nm 2 Solid ball sol and acid fluorosilicone sol are prepared according to SiO 2 Molar ratio 7:3 mixing and aging for 2 days to obtain uniform and stable mixed sol.
(3) Coating is plated by adopting a dipping-pulling method, the pulling speed is 1000 mu m/s, the dipping time is 360s, and then the coating is placed in a baking oven at 200 ℃ for curing for 1h, so that the wear-resistant hydrophobic self-cleaning anti-reflection coating is prepared. The average light transmittance of the coating in the visible light range can reach 94.31%, the water contact angle is 127%, the hysteresis angle is 4%, the hardness is 5H, and the average light transmittance of the alcohol cotton ball after 1000 times of friction is 92.98%.
Example 6
Acidic fluorosilicon sol and SiO 2 The solid sphere sol was prepared as in example 1.
(1) SiO of 50nm 2 Solid ball sol and acid fluorosilicone sol are prepared according to SiO 2 Molar ratio 7:3 mixing and aging for 2 days to obtain uniform and stable mixed sol.
(2) Coating is plated by adopting a dipping-pulling method, the pulling speed is 1500 mu m/s, the dipping time is 360s, and then the coating is prepared by placing the coating in a baking oven at 200 ℃ for curing for 1h. The average light transmittance of the coating in the visible light range can reach 94.57%, the water contact angle is 127%, the hysteresis angle is 4%, the hardness is 6H, and the average light transmittance of the alcohol cotton ball after 1000 times of friction is 93.10%.
Example 7
Preparation of acidic fluorosilicone Sols the same procedure as in example 1
(1) Absolute ethyl alcohol (EtOH) is used as solvent, ammonia (NH) 4 OH) as a catalyst, tetraethyl orthosilicate (TEOS) as a silicon source, and preparing 20nm SiO by a sol-gel method with vigorous stirring at 25 ℃ for 20min and aging for 2 days 2 Solid pellet sol, siO 2 Placing the solid ball sol in a fume hood, vigorously stirring to remove ammonia, and supplementing solvent after ammonia removal until the mass is equal to that before ammonia removal;
wherein, TEOS: etOH: NH (NH) 4 The molar ratio of OH is 2:38:0.27.
(2) SiO of 20nm 2 Solid ball sol and acid fluorosilicone sol are prepared according to SiO 2 Molar ratio 7:3 mixing and aging for 2 days to obtain uniform and stable mixed sol.
(3) Coating is plated by adopting a dipping-pulling method, the pulling speed is 1000 mu m/s, the dipping time is 360s, and then the coating is prepared by placing the coating in a baking oven at 200 ℃ for curing for 1h. The average light transmittance of the coating in the visible light range can reach 93.67%, the water contact angle is 119 degrees, the hysteresis angle is 13 degrees, the hardness is 6H, and the average light transmittance is 93.00% after the alcohol cotton ball is rubbed 1000 times.
Example 8
Preparation of acidic fluorosilicone Sols the same procedure as in example 1
(1) Absolute ethyl alcohol (EtOH) is used as solvent, ammonia (NH) 4 OH) as a catalyst, tetraethyl orthosilicate (TEOS) as a silicon source, and preparing 100nm SiO by a sol-gel method with vigorous stirring at 25 ℃ for 20min, aging for 2 days 2 Solid pellet sol, siO 2 Placing the solid ball sol in a fume hood, vigorously stirring to remove ammonia, and supplementing solvent after ammonia removal until the mass is equal to that before ammonia removal;
wherein, TEOS: etOH: NH (NH) 4 The molar ratio of OH is 1:38:1.8.
(2) 100nm of SiO 2 Solid ball sol and acid fluorosilicone sol are prepared according to SiO 2 Molar ratio 7:3 mixing and aging for 2 days to obtain uniform and stable mixed sol.
(3) Coating is plated by adopting a dipping-pulling method, the pulling speed is 1000 mu m/s, the dipping time is 360s, and then the coating is prepared by placing the coating in a baking oven at 200 ℃ for curing for 1h. The average light transmittance of the coating in the visible light range can reach 92.21%, the water contact angle is 133 degrees, the hysteresis angle is 3 degrees, the hardness is 4H, and the average light transmittance is 92.00% after the alcohol cotton ball is rubbed 1000 times.
Example 9
(1) Absolute ethyl alcohol (EtOH) is used as a solvent, concentrated hydrochloric acid (HCl) is used as a catalyst, tetraethyl orthosilicate (TEOS) and perfluorodecyl triethoxysilane (FAS-17) are used as silicon sources, and an acidic fluorosilicone sol is prepared by a sol-gel method and aged;
wherein Si Total (TEOS/FAS-17): etOH: the molar ratio of HCl is 1:34:0.65, aging time is 5 days;
(2) SiO of 50nm 2 Solid ball sols (same as in example 1) and acidic fluorosilicone sols (TEOS/FAS-17) are prepared according to SiO 2 Molar ratio 7:3 mixing and aging for 2 days to obtain uniform and stable mixed sol.
(3) Coating is plated by adopting a dipping-pulling method, the pulling speed is 1000 mu m/s, the dipping time is 360s, and then the coating is prepared by placing the coating in a baking oven at 200 ℃ for curing for 1h. The average light transmittance of the coating in the visible light range can reach 93.91%, the water contact angle is 127%, the hysteresis angle is 4 degrees, the hardness is 5H, and the average light transmittance is 92.28% after the alcohol cotton ball is rubbed 1000 times.
Comparative example 1
Acidic fluorosilicon sol and SiO 2 The solid sphere sol was prepared as in example 1.
(1) SiO of 50nm 2 Solid ball sol and acid fluorosilicone sol are prepared according to SiO 2 Molar ratio 7:3 mixing and aging for 2 days to obtain uniform and stable mixed sol.
(2) The coating is plated by adopting a spraying method, and then the coating is placed in a baking oven at 200 ℃ to be cured for 1h, so that the wear-resistant hydrophobic self-cleaning anti-reflection coating is prepared. The average light transmittance of the coating in the visible light range can reach 93.45%, the water contact angle is 127%, the hysteresis angle is 4 degrees, the hardness is 4H, and the average light transmittance is 92.00% after the alcohol cotton ball is rubbed 1000 times.
Comparative example 2
(1) Absolute ethyl alcohol (EtOH) is used as a solvent, concentrated hydrochloric acid (HCl) is used as a catalyst, tetraethyl orthosilicate (TEOS) is used as a silicon source, an acidic silica sol is prepared by a sol-gel method, and the acidic silica sol is aged;
wherein, si: etOH: the molar ratio of HCl is 1:38:0.72, aging time is 5 days;
(2) SiO of 50nm 2 Solid sphere sol (same as example 1) and acidic silica sol according to SiO 2 Molar ratio 7:3 mixing and aging for 2 days to obtain uniform and stable mixed sol.
(3) Coating is plated by adopting a dipping-pulling method, the pulling speed is 1000 mu m/s, the dipping time is 360s, and then the coating is prepared by placing the coating in a baking oven at 200 ℃ for curing for 1h. The average light transmittance of the coating in the visible light range can reach 94.22%, the water contact angle is 55 degrees, the hardness is 4H, and the average light transmittance is 92.00% after the alcohol cotton ball is rubbed 1000 times.
Comparative example 3
Acidic fluorosilicon sol and SiO 2 The solid sphere sol was prepared as in example 1.
(1) SiO of 50nm 2 Solid ball sol and acid fluorosilicone sol are prepared according to SiO 2 Molar ratio 7:3, mixing to obtain uniform and stable mixed sol.
(2) Coating is plated by adopting a dipping-pulling method, the pulling speed is 1000 mu m/s, the dipping time is 360s, and then the coating is placed in a baking oven at 200 ℃ for curing for 1h, so that the wear-resistant hydrophobic self-cleaning anti-reflection coating is prepared. The average light transmittance of the coating in the visible light range can reach 94.79%, the water contact angle is 93 degrees, the hysteresis angle is 30 degrees, the hardness is 4H, and the average light transmittance is 92.00% after the alcohol cotton ball is rubbed 1000 times.
The examples are preferred embodiments of the present invention, but the present invention is not limited to the above-described embodiments, and any obvious modifications, substitutions or variations that can be made by one skilled in the art without departing from the spirit of the present invention are within the scope of the present invention.

Claims (10)

1. The preparation method of the wear-resistant hydrophobic self-cleaning anti-reflection coating is characterized by comprising the following steps of:
(1) Preparing acidic fluorosilicone sol by a sol-gel method, and aging for later use; preparing solid silica ball sol by sol-gel method;
(2) SiO is made of 2 Placing the solid ball sol in a fume hood, vigorously stirring to remove ammonia, and supplementing solvent after ammonia removal until the mass is equal to that before ammonia removal; siO is made of 2 Solid ball sol and acid fluorosilicone sol are prepared according to SiO 2 Mixing and aging the mixture in the molar ratio to prepare stable and uniform mixed sol;
(3) And (3) plating the mixed sol obtained in the step (2) on a glass substrate by adopting a dipping and pulling method, and then placing the glass substrate into an oven for curing to obtain the wear-resistant hydrophobic self-cleaning anti-reflection coating.
2. The method for preparing the wear-resistant hydrophobic self-cleaning anti-reflection coating according to claim 1, wherein the method comprises the following steps: in the step (1), absolute ethyl alcohol (EtOH) is used as a solvent, concentrated hydrochloric acid (HCl) is used as a catalyst, tetraethyl orthosilicate (TEOS) and fluorosilane are used as silicon sources, and an acidic fluorosilicone sol is prepared by a sol-gel method.
3. The method for preparing the wear-resistant hydrophobic self-cleaning anti-reflection coating according to claim 2, which is characterized in that: si (Si) Total (S) (TEOS/FAS-9): etOH: the molar ratio of HCl is 1:33-34:0.63-0.65; the molar ratio of tetraethyl orthosilicate (TEOS) to fluorine-containing silane is 8-10:1-2; the fluorine-containing silane is nonafluorohexyl triethoxysilane (FAS-9) or perfluorodecyl triethoxysilane (FAS-17).
4. The method for preparing the wear-resistant hydrophobic self-cleaning anti-reflection coating according to claim 1, wherein the method comprises the following steps: step (1) uses absolute ethyl alcohol (EtOH) as solvent, ammonia (NH) 4 OH) asCatalyst, tetraethyl orthosilicate (TEOS) is used as a silicon source, and a sol-gel method is adopted to prepare SiO 2 Solid pellet sol.
5. The method for preparing the wear-resistant hydrophobic self-cleaning anti-reflection coating according to claim 4, which is characterized in that: TEOS: etOH: NH (NH) 4 The molar ratio of OH is 1-2:38:0.27-1.8, and the particle size of the prepared silica solid sphere sol is 20-100nm.
6. The method for preparing the wear-resistant hydrophobic self-cleaning anti-reflection coating according to claim 1, wherein the method comprises the following steps: step (1) preparing acidic silica-fluorine sol by vigorously stirring in a water bath at 30 ℃ for 120 min; the aging time was 5 days.
7. The method for preparing the wear-resistant hydrophobic self-cleaning anti-reflection coating according to claim 1, wherein the method comprises the following steps: and (3) vigorously stirring at 25 ℃ for 20min, and aging for 2 days to prepare the silica solid sphere sol.
8. The method for preparing the wear-resistant hydrophobic self-cleaning anti-reflection coating according to claim 1, wherein the method comprises the following steps: siO in step (2) 2 SiO in solid ball sol and acid fluorine silicon sol 2 The molar ratio of (2) is 9:1-6:4.
9. the method for preparing the wear-resistant hydrophobic self-cleaning anti-reflection coating according to claim 1, wherein the method comprises the following steps: the lifting speed of the dipping and lifting in the step (3) is 1000-1500 mu m/s, the dipping time is 360s, and the curing is carried out for 1h in an oven at 200 ℃.
10. A wear resistant hydrophobic self-cleaning anti-reflective coating prepared by the method of any one of claims 1 to 9, wherein said coating has an average light transmittance of 92 to 97% in the visible range, a water contact angle of 116 to 133 °, a hysteresis angle of 3 to 15 °, a hardness of 4 to 8H, and an average light transmittance of greater than 92% after 1000 rubs with an alcoholic cotton ball.
CN202310548375.0A 2023-05-16 2023-05-16 Wear-resistant hydrophobic self-cleaning anti-reflection coating and preparation method thereof Pending CN116621465A (en)

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