Preparation method of glass surface anti-reflection self-cleaning structure and application thereof

Abstract

The application relates to the technical field of C03C, in particular to a preparation method of a glass surface anti-reflection self-cleaning structure and application thereof, which at least comprises the following steps: (1) glass substrate pretreatment: washing a glass substrate and then blowing dry; (2) glass substrate corrosion: adopting etching liquid to corrode one side of the glass substrate treated in the step (1) to form a glass porous layer; (3) amorphous TiO2 deposition: placing the glass substrate treated in the step (2) into a TiCl4 solution to perform a deposition reaction; (4) removal of amorphous TiO2 on the outer surface: placing the glass substrate treated in the step (3) into contact with a hydrofluoric acid aqueous solution, then washing and blowing dry; (5) amorphous TiO2 calcination: placing the glass substrate treated in the step (4) into a muffle furnace to perform calcination, and the glass surface structure prepared by the method has the functions of anti-reflection, super-hydrophobic self-cleaning and titanium dioxide photocatalytic self-cleaning.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of C03C, in particular to a preparation method of a glass surface anti-reflection self-cleaning structure and application thereof. BACKGROUND

[0002] When light enters glass from air, due to the large difference in refractive index between the two, light will be strongly reflected at the glass / air interface, which is not conducive in some application scenarios. For example, the surface of a photovoltaic system is usually covered with tempered photovoltaic glass, which is one of the important factors that determine the photoelectric conversion efficiency of solar cells. For ordinary glass, more than 4% of the incident light will be reflected at the glass / air interface, and as the use time increases, the surface will be contaminated, further reducing the transmittance of incident light. Therefore, it is necessary to develop a glass coating or structure with anti-reflection performance or even self-cleaning function.

[0003] At present, the anti-reflection function of glass can be realized by forming several layers of anti-reflection coating structure on the surface of glass through sol-gel method or top-down photolithography technology. This method has low cost, but requires the synergistic effect of multiple coatings, the process is complex, and the thickness of the coating is very high. The coating prepared by sol-gel method is often not strong enough, and the anti-peeling performance is insufficient, and the process is relatively simple, but it needs to use electron beam lithography and other equipment, which is very costly. For example, Chinese patent application (application number CN115763580A) discloses a transparent material surface self-cleaning anti-reflection coating and a preparation method thereof, which specifically uses sol-gel method to realize the anti-reflection function of glass. Therefore, it is necessary to develop a new preparation method for glass surface anti-reflection structure.

[0004] The self-cleaning function of glass can be achieved through the super-hydrophobic property or photocatalytic ability of the surface. Super-hydrophobic surface utilizes the low surface energy state of the surface, so that pollutants are not easy to adhere to the glass surface, and the adhered pollutants are more easily removed under the scouring of rainwater; photocatalysis utilizes the production of active reaction substances such as oxygen free radicals, oxygen anions and strong oxidizing holes by wide-bandgap semiconductors (such as TiO2) under light to degrade pollutants, thereby achieving self-cleaning. However, due to the super-hydrophilic property of TiO2, super-hydrophobic and photocatalytic self-cleaning are often incompatible. SUMMARY

[0005] In order to solve the above problems, the present application provides a preparation method of a glass surface anti-reflection self-cleaning structure. The glass surface structure prepared by the method has anti-reflection function, super-hydrophobic self-cleaning and titanium dioxide photocatalytic self-cleaning function. The glass with the structure has no obvious decrease in transmittance during outdoor use, which has important significance in the field of photovoltaic glass and the like.

[0006] The application provides a preparation method of a glass surface antireflection self-cleaning structure.

[0007] (1) glass substrate pretreatment: washing and drying the glass substrate;

[0008] (2) glass substrate etching: etching one side of the glass substrate treated in step (1) to form a glass porous layer;

[0009] (3) amorphous TiO2 deposition: placing the glass substrate treated in step (2) into a TiCl4 solution for deposition reaction;

[0010] (4) removal of amorphous TiO2 on the outer surface: contacting the glass substrate treated in step (3) with an aqueous hydrofluoric acid solution, washing and drying;

[0011] (5) amorphous TiO2 calcination: placing the glass substrate treated in step (4) into a muffle furnace for calcination.

[0012] As a preferred technical scheme, the step (1) glass substrate pretreatment is specifically: sequentially placing the glass substrate into a washing powder solution, deionized water, acetone and ethanol for ultrasonic cleaning for 15 minutes, and then blowing dry with a nitrogen gas flow.

[0013] As a preferred technical scheme, the step (2) glass substrate etching is specifically: sticking one side of the glass substrate treated in step (1) with a high-temperature-resistant adhesive tape (to avoid etching liquid corrosion), then placing it into an etching liquid and heating for reaction, and then taking out the glass substrate, washing with deionized water and blowing dry with a nitrogen gas flow.

[0014] Preferably, the etching liquid in step (2) is an aqueous NaHCO3 solution, and the concentration of the aqueous NaHCO3 solution is 0.1-1 mol / L; preferably, the heating reaction temperature is 80-120℃, and the heating reaction time is 10-30 h. Preferably, the etching liquid in step (2) is an aqueous NaHCO3 solution, and the concentration of the aqueous NaHCO3 solution is 0.3-0.5 mol / L; preferably, the heating reaction temperature is 100-120℃, and the heating reaction time is 15-20 h.

[0015] The method of the present application is to reduce the reflectivity of glass and improve its self-cleaning performance as the purpose, a new type of sodium calcium glass surface anti-reflective self-cleaning structure preparation method is developed. By using sodium bicarbonate aqueous solution as etching solution to corrode the glass surface, a porous layer with non-uniformly distributed pore size is formed; Especially when the glass substrate is in the concentration of 0.1-1mol / L NaHCO3 aqueous solution, the heating reaction temperature and time are controlled, the porous structure with continuously changing pore size and decreasing pore size with increasing depth is formed, which effectively reduces the reflectivity of glass and endows the glass with super-hydrophobic property. The inventor analyzes the reason: NaHCO3 aqueous solution is alkaline, which can destroy the silicon-oxygen skeleton in the glass, and make SiO2 dissolved in the solution, but the pH, temperature and cation type of NaHCO3 aqueous solution affect the corrosion rate of the glass surface, the inventor controls the concentration of NaHCO3 aqueous solution, reaction temperature and time at the same time, forms the porous structure with continuously changing pore size and decreasing pore size with increasing depth, due to the change trend of the pore size with the depth, the refractive index of the glass increases gradually from the surface to the inside, forming a refractive index gradient layer, so the reflectivity of the glass can be reduced (the transmittance is increased). In addition, the porous structure also causes a rough surface, so the glass also has super-hydrophobic property.

[0016] As a preferred technical solution, the step (3) of depositing amorphous TiO2 is specifically: the glass substrate treated in step (2) is placed in a glass culture dish, ensuring that the glass porous layer faces up, TiCl4 solution is poured into the culture dish to ensure that the glass porous layer of the glass substrate is completely covered; the culture dish is placed in an oven for deposition reaction, then the reaction solution is poured out, washed with deionized water and dried with nitrogen gas flow, and the high-temperature resistant adhesive tape is removed.

[0017] Preferably, the preparation method of the TiCl4 solution in step (3) is: 200mL deionized water in a beaker is frozen into ice, 3-8mL TiCl4 is slowly added to the ice surface, and the TiCl4 solution is prepared after the ice is completely melted.

[0018] Preferably, the temperature of the deposition reaction in step (3) is 60-90℃, and the time is 60-100min. Preferably, the temperature of the deposition reaction in step (3) is 65-75℃, and the time is 65-75min.

[0019] As a preferred technical solution, the step (4) of removing amorphous TiO2 on the outer surface is specifically: the glass porous layer of the glass substrate treated in step (3) faces down, and is immediately washed with deionized water and dried with nitrogen gas flow after being treated with hydrofluoric acid aqueous solution.

[0020] Preferably, the concentration of the aqueous hydrofluoric acid solution in step (4) is 1-100 mmol / L, and the contact treatment time is 1-10 s. Preferably, the concentration of the aqueous hydrofluoric acid solution in step (4) is 1-10 mmol / L, and the contact treatment time is 2-5 s.

[0021] The method provided by the application can place the glass substrate treated in step (2) in a TiCl4 solution, control the deposition reaction temperature and time, hydrolyze TiCl4 and deposit amorphous TiO2 on the inner and outer surfaces of the porous structure of the glass surface, and then use an aqueous hydrofluoric acid solution to corrode the TiO2 on the outer surface of the porous structure of the glass (the TiO2 on the inner surface is reserved), so that the porous structure with TiO2 deposited on the inner surface is obtained. Since the amount of TiO2 deposited is small and on the inner surface, the glass surface structure still has good antireflection and super-hydrophobic properties.

[0022] As a preferred technical solution, the calcination of the amorphous TiO2 in step (5) is specifically as follows: the glass substrate treated in step (4) is placed in a muffle furnace, and is calcined at 450-500 DEG C for 1 hour, so that the amorphous TiO2 is obtained.

[0023] The method provided by the application can enhance the crystallinity of TiO2 by calcining the glass substrate with the porous structure with TiO2 deposited on the inner surface after treatment, so that the calcined crystalline TiO2 can endow the glass with the performance of photocatalytic degradation of pollutants, and endow the glass with the function of titanium dioxide photocatalytic self-cleaning.

[0024] Advantages

[0025] 1. The application provides a preparation method of a glass surface antireflection self-cleaning structure, and the glass surface structure prepared by the method has the functions of antireflection, super-hydrophobic self-cleaning and titanium dioxide photocatalytic self-cleaning, and the glass with the structure has no obvious decrease in transmittance during outdoor use, which has important significance in the field of photovoltaic glass and the like.

[0026] 2. The method provided by the application can corrode the glass surface by using an aqueous sodium bicarbonate solution as an etching liquid to form a porous layer with non-uniformly distributed pore diameters; especially when the glass substrate is in an aqueous NaHCO3 solution with a concentration of 0.1-1 mol / L, the heating reaction temperature and time are controlled to form a porous structure with continuously changing pore diameters and decreasing pore diameters with increasing depth, so that the reflectivity of the glass is effectively reduced, and the glass is endowed with super-hydrophobic properties.

[0027] 3、The method provided by the application, the glass substrate treated in step (2) is placed in a TiCl4 solution, by controlling the deposition reaction temperature and time, TiCl4 is hydrolyzed and amorphous TiO2 is deposited on the inner and outer surfaces of the porous structure of the glass surface, then the TiO2 on the outer surface of the porous structure of the glass is corroded by using a hydrofluoric acid aqueous solution (the TiO2 on the inner surface is reserved), and the porous structure with TiO2 deposited on the inner surface is obtained.

[0028] 4、The method provided by the application, by calcining the glass substrate with the porous structure with TiO2 deposited on the inner surface after treatment, the crystallinity of TiO2 is enhanced, and the calcined crystalline TiO2 can endow the glass with the performance of photocatalytic degradation of pollutants and the function of titanium dioxide photocatalytic self-cleaning.

[0029] 5、The glass surface anti-reflective self-cleaning structure provided by the application has good anti-reflective and super-hydrophobic properties due to the small amount of TiO2 deposited on the inner surface. BRIEF DESCRIPTION OF DRAWINGS

[0030] Figure 1 A flowchart of a preparation method of a glass surface anti-reflective self-cleaning structure provided by Example 1 of the application.

[0031] Figure 2 The transmittance spectrum of the glass sample prepared in Example 1 and Comparative Examples 1 and 2 after being placed outdoors for 30 days and washed with deionized water is shown in the figure, and the spectral lines a, b and c correspond to Example 1, Comparative Example 1 and Comparative Example 2, respectively. DETAILED DESCRIPTION

[0032] Example 1

[0033] Reference Figure 1 Example 1 of the application provides a preparation method of a glass surface anti-reflective self-cleaning structure, which comprises the following steps:

[0034] (1) Sodium-calcium glass (2x5cm, thickness 1mm, commercially available) is ultrasonically cleaned with a laundry detergent solution, deionized water, acetone (commercially available, AR) and ethanol (commercially available, AR) for 15 minutes, and then dried by blowing nitrogen gas;

[0035] (2) One side of the glass substrate treated in step (1) is pasted with a high-temperature-resistant adhesive tape (to avoid corrosion of the etching solution), and then placed in an etching solution and heated for reaction, and then the glass substrate is taken out, washed with deionized water and dried by blowing nitrogen gas;

[0036] (3) Put the glass substrate treated in step (2) into a glass culture dish, make sure the glass porous layer faces up, pour TiCl4 solution into the culture dish to make sure the glass porous layer of the glass substrate is completely covered; put the culture dish into an oven to carry out deposition reaction, then pour out the reaction solution, rinse with deionized water and dry with nitrogen gas flow, and tear off the high-temperature resistant adhesive tape;

[0037] (4) Put the glass substrate treated in step (3) with the glass porous layer facing down, and immediately after contacting with the hydrofluoric acid aqueous solution, rinse with deionized water and dry with nitrogen gas flow;

[0038] (5) Put the glass substrate treated in step (4) into a muffle furnace, calcine at 450℃ for 1 hour, and then obtain.

[0039] In step (2), the etching solution is NaHCO3 aqueous solution, and the concentration of the NaHCO3 aqueous solution is 0.5 mol / L; the heating reaction temperature is 120℃, and the heating reaction time is 15 h.

[0040] In step (3), the preparation method of the TiCl4 solution is as follows: freeze 200 mL deionized water in a beaker into ice, slowly drop 4.5 mL TiCl4 onto the ice surface, and prepare the TiCl4 solution after the ice completely melts.

[0041] In step (3), the temperature of the deposition reaction is 75℃, and the time is 65 min.

[0042] In step (4), the concentration of the hydrofluoric acid aqueous solution is 10 mmol / L, and the contacting treatment time is 2 s.

[0043] Example 2

[0044] Example 2 of the present application provides a preparation method of a glass surface anti-reflection self-cleaning structure, and the specific implementation manner is the same as that of Example 1, except that:

[0045] In step (2), the etching solution is NaHCO3 aqueous solution, and the concentration of the NaHCO3 aqueous solution is 0.3 mol / L; the heating reaction temperature is 100℃, and the heating reaction time is 20 h.

[0046] In step (3), the temperature of the deposition reaction is 65℃, and the time is 75 min.

[0047] In step (4), the concentration of the hydrofluoric acid aqueous solution is 1 mmol / L, and the contacting treatment time is 5 s.

[0048] Comparative Example 1

[0049] Comparative Example 1 of the present application provides a preparation method of a glass surface anti-reflection self-cleaning structure, which comprises the following steps:

[0050] (1) Sodium-calcium glass (2x5cm, thickness 1mm, commercially available) was ultrasonically cleaned with laundry detergent solution, deionized water, acetone (commercially available, AR) and ethanol (commercially available, AR) respectively for 15 minutes, and then dried with nitrogen gas flow;

[0051] (2) One side of the glass substrate treated in step (1) was taped with high-temperature-resistant tape (to avoid corrosion of etching solution), and then placed in an etching solution and heated for reaction, and then the glass substrate was taken out, washed with deionized water and dried with nitrogen gas flow.

[0052] The etching solution in step (2) is a NaHCO3 aqueous solution, and the concentration of the NaHCO3 aqueous solution is 0.5 mol / L; the heating reaction temperature is 120℃, and the heating reaction time is 15h.

[0053] Comparative Example 2

[0054] The comparative example 2 of the present application provides a preparation method of a glass surface anti-reflection self-cleaning structure, comprising the following steps:

[0055] (1) Sodium-calcium glass (2x5cm, thickness 1mm, commercially available) was ultrasonically cleaned with laundry detergent solution, deionized water, acetone (commercially available, AR) and ethanol (commercially available, AR) respectively for 15 minutes, and then dried with nitrogen gas flow;

[0056] (2) One side of the glass substrate treated in step (1) was taped with high-temperature-resistant tape (to avoid corrosion of etching solution), and then placed in an etching solution and heated for reaction, and then the glass substrate was taken out, washed with deionized water and dried with nitrogen gas flow.

[0057] (3) The glass substrate treated in step (2) was placed in a glass culture dish, ensuring that the glass porous layer was upward, and TiCl4 solution was poured into the culture dish to ensure that the glass porous layer of the glass substrate was completely covered; the culture dish was placed in an oven for deposition reaction, and then the reaction solution was poured out, washed with deionized water and dried with nitrogen gas flow, and the high-temperature-resistant tape was removed;

[0058] (4) The glass porous layer of the glass substrate treated in step (3) was placed downward, and immediately after being treated with hydrofluoric acid aqueous solution, it was washed with deionized water and dried with nitrogen gas flow.

[0059] Comparative Example

[0060] The comparative example of the present application is untreated glass, and sodium-calcium glass (2x5cm, thickness 1mm, commercially available) was ultrasonically cleaned with laundry detergent solution, deionized water, acetone (commercially available, AR) and ethanol (commercially available, AR) respectively for 15 minutes, and then dried with nitrogen gas flow.

[0061] Performance test method

[0062] 1. The reflectance 1 and transmittance 1 of the glass samples provided by the examples, comparative examples and control examples in the wavelength range of 400-800 nm were tested by using a UV-visible spectrophotometer (Shimadzu UV2600), 5 samples were tested in parallel, and the test results were averaged (average reflectance 1 and average transmittance 1). The water contact angle 1 of the glass samples provided by the examples, comparative examples and control examples was tested by using a contact angle measuring instrument (Bouyoukou Theta Flow), 5 samples were tested in parallel, and the test results were averaged (average contact angle 1). The results are recorded in Table 1.

[0063] 2. The glass samples provided by the examples, comparative examples and control examples were placed outdoors for 30 days, then dropwise washed with deionized water at a height of about 0.5 m from the glass sample, and after natural drying, the reflectance 2, transmittance 2 and water contact angle 2 of the glass sample in the wavelength range of 400-800 nm were tested, 5 samples were tested in parallel, and the test results were averaged (average reflectance 2, average transmittance 2 and average water contact angle 2). The results are recorded in Table 1. The transmittance spectrum of the glass sample prepared by Example 1 and Comparative Example 1 and Control Example after being placed outdoors for 30 days and washed with deionized water is shown in Figure 2 .

[0064] Table 1,

[0065]

Claims

1. A method of making a glass surface antireflective self-cleaning structure, characterized in that, At least comprising the following steps: (1) glass substrate pretreatment: washing and drying the glass substrate; (2) etching of the glass substrate: etching one side of the glass substrate treated in step (1) to form a glass porous layer; (3) deposition of amorphous TiO2: placing the glass substrate treated in step (2) into a TiCl4 solution for deposition reaction; (4) removal of amorphous TiO2 on the outer surface: contacting the glass substrate treated in step (3) with an aqueous hydrofluoric acid solution, then washing and drying; (5) calcination of amorphous TiO2: placing the glass substrate treated in step (4) into a muffle furnace for calcination, and obtaining the product; In step (2), the glass substrate treated in step (1) is pasted with a high-temperature-resistant tape on one side, then placed into an etching solution and heated for reaction, and then taken out, washed with deionized water and dried with nitrogen gas flow; the etching solution in step (2) is an aqueous NaHCO3 solution, and the concentration of the aqueous NaHCO3 solution is 0.1-1 mol / L; the heating reaction temperature is 80-120℃, and the heating reaction time is 10-30 h; In step (3), the glass substrate treated in step (2) is placed into a glass culture dish with the glass porous layer facing up, TiCl4 solution is poured into the culture dish to ensure that the glass porous layer of the glass substrate is completely covered, and then the culture dish is placed into an oven for deposition reaction, after which the reaction solution is poured out, washed with deionized water and dried with nitrogen gas flow, and the high-temperature-resistant tape is removed; the deposition reaction temperature in step (3) is 60-90℃, and the time is 60-100 min; In step (4), the glass porous layer of the glass substrate treated in step (3) is placed with the glass porous layer facing down, and then immediately washed with deionized water and dried with nitrogen gas flow after contacting with an aqueous hydrofluoric acid solution; the concentration of the aqueous hydrofluoric acid solution in step (4) is 1-10 mmol / L, and the contacting time is 2-5 s.

2. The method of producing a glass surface antireflection self-cleaning structure according to claim 1, wherein In step (1), the glass substrate is sequentially placed into a washing powder solution, deionized water, acetone and ethanol for ultrasonic cleaning for 15 min, and then dried with nitrogen gas flow.

3. The method of producing a glass surface antireflection self-cleaning structure according to claim 1, wherein In step (3), the TiCl4 solution is prepared by freezing 200 mL of deionized water in a beaker into ice, slowly adding 3-8 mL of TiCl4 to the ice surface, and then preparing the TiCl4 solution after the ice completely melts.

4. Use of a method for the production of a glass surface antireflection self-cleaning structure according to any one of claims 1-3, characterized in that, The application is applied to the preparation of a glass surface anti-reflection self-cleaning structure.

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