CN110734229A - A kind of superhydrophobic antireflection antireflection frosted glass and preparation method thereof - Google Patents

Abstract

The invention provides super-hydrophobic high-transmittance antireflection frosted glass and a preparation method thereof, which comprises the steps of preparing a frosting solution by using soda-lime glass as a substrate and using sulfuric acid and fluoride-containing salts, frosting for times at room temperature to obtain a frosting glass substrate with proper roughness, and heating the frosting glass substrate for 1-2 hours at the temperature of 150 ℃ in air after being treated by a surface modifier 1H,1H,2H, 2H-perfluorodecyl triethoxysilane (FDTES) to obtain the high-transmittance antireflection frosting glass with excellent hydrophobic property.

Description

A kind of superhydrophobic antireflection antireflection frosted glass and preparation method thereof

technical field

The invention belongs to the field of preparation of functionalized glass, in particular to a superhydrophobic, antireflection, antireflection frosted glass and a preparation method thereof.

Background technique

Frosted glass is a kind of functional glass with anti-reflection effect obtained by processing. The use of frosting liquid to chemically corrode ordinary glass can form a micron-level rough structure on the glass surface, which has the effect of anti-glare and anti-reflection. In daily life and architectural decoration applications, traditional frosted glass often uses strong acid as the frosting liquid, which will cause harm and pollution to the human body and the environment; and the surface after frosting is relatively rough, which reduces reflection while achieving anti-reflection. The light transmittance of glass greatly limits the application range of frosted glass.

In addition, in the application of decorative glass in high-rise buildings, the cleaning problem of frosted glass also has a great potential safety hazard. Now it is often used to coat or coat the surface of frosted glass to make it hydrophobic and oleophobic to achieve self-cleaning of the glass. However, the glass surface obtained in this way has poor bonding with the functional film layer, and has problems such as complicated process, short service life, high cost, easy pollution to the environment, and harm to human health. Therefore, the functionalization of glass surface needs to be realized by a process with good bonding, simple operation and excellent effect.

SUMMARY OF THE INVENTION

In view of the problems existing in the prior art, the present invention provides a superhydrophobic, antireflection, antireflection frosted glass and a preparation method thereof, which can ensure the antireflection performance of the glass and simultaneously improve the light transmittance and hydrophobicity of the frosted glass.

The present invention is achieved through the following technical solutions:

A preparation method of superhydrophobic antireflection and antireflection frosted glass, comprising:

(1) Preparation of frosting liquid: a mixed solution of Na ₂ SiF ₆ , H ₂ C ₂ O ₄ , NH ₄ F, NH ₄ HF ₂ , (NH ₄ ) ₂ SO ₄ , CaF ₂ , KF and K ₂ SO ₄ Dissolve the salt in water, stir evenly to obtain liquid B; adjust the pH of liquid B to 2.5-7, and obtain frosting liquid after aging;

(2) Frosting etching: After the glass is waterproofed on one side, it is placed in a frosting liquid to frost one side, and then the glass surface is cleaned to obtain frosted glass;

(3) Surface modification: The surface modifier 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane was prepared into liquid C with methanol as solvent, and the frosted glass was placed in liquid C to react for 8-10h , the reaction temperature is 60-65°C; then the frosted glass is heated in liquid C at 120-150°C for 1-2 hours, and then cleaned and dried to obtain superhydrophobic, antireflection, and antireflection frosted glass.

Preferably, in step (1), in terms of mass percentage, the composition of liquid B is: 2%-7% Na ₂ SiF ₆ , 2%-3% H ₂ C ₂ O ₄ , 69%-73% NH _4F , 4%-5% NH4HF2, ₂ %-3% ( _NH4 ) _2SO4 , ₇ %-8% _CaF2 , ₄ %-5% KF, 2%-3% K ₂ SO ₄ , balance deionized water.

Preferably, in step (1), the pH value of solution B is adjusted to 2.5-7 by using H ₂ SO ₄ .

Preferably, in step (1), the curing temperature is 20°C-30°C, and the curing time is 6-8h.

Preferably, before the step (2), a glass cleaning step is also included: prepare a liquid A with the singalite reagent and water; let the glass stand in the liquid A for 10-30min, stir in the film-removing liquid for 20-30min, and use water accordingly. Clean with ultrasonic device and dry.

Preferably, in step (2), the frosting time is 3-30min.

Preferably, in step (3), the mass concentration of 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane in liquid C is 2-10%.

The superhydrophobic antireflection and antireflection frosted glass obtained by the preparation method.

Compared with the prior art, the present invention has the following beneficial technical effects:

First, the present invention uses mixed dissolved salt to replace traditional hydrofluoric acid for frosting etching, which reduces harm and pollution to human body and the environment, and the frosting liquid can be recycled, which is more in line with the modern production concept of environmental protection and conservation.

Second, the present invention directly uses the mixed dissolved salt of fluorine-containing salt, sulfuric acid and water, and the hydrofluoric acid produced by the reaction by adjusting the raw material formula and preparation process, to frost and corrode the glass, so that the complex fluorosilicic acid on the surface of the glass is formed. It interacts with the hydroxide produced by hydrolysis to form fluorosilicate particles such as NaSiF ₆ and K ₂ SiF ₆ . Due to the uniform size and distribution of these particles, they are firmly attached to the glass surface, preventing further erosion of hydrofluoric acid and forming a honeycomb structure with a size of about 1 to 3 μm. It is captured and cannot be reflected, which reduces the reflectivity and achieves the effect of anti-glare and anti-reflection; while the light passes through the glass through the reflection and refraction between the honeycomb peaks of the glass, which greatly improves the transmittance of the glass. . Subsequently, the frosted glass was further corroded by perfluorinated surface modifier, which reduced the low surface energy of the rough surface and significantly improved the hydrophobicity.

Third, the superhydrophobic, antireflection, antireflection frosted glass provided by the present invention has a certain self-cleaning ability and has a wider application prospect.

Description of drawings

Figure 1 shows the contact angle between the surface of the prepared superhydrophobic antireflection and antireflection frosted glass and water droplets.

FIG. 2 is a SEM image of the surface of the prepared superhydrophobic antireflection and antireflection frosted glass.

FIG. 3 is a comparison diagram of light transmittance between the prepared superhydrophobic, antireflection, antireflection frosted glass (frosted) and ordinary glass (blank).

FIG. 4 is a comparison chart of the absorbance of the prepared superhydrophobic, antireflection, antireflection frosted glass (frosted) and ordinary glass (blank).

Detailed ways

The present invention will be further described in detail below in conjunction with specific embodiments, which are to explain rather than limit the present invention.

The preparation method of superhydrophobic antireflection antireflection frosted glass according to the present invention comprises the following steps:

(1) Cleaning of the glass substrate: Prepare solution A with the selenium reagent and deionized water in a molar ratio of 1:1; put the glass substrate in solution A for 10-30min, stir in the removing solution for 20-30min, and use it accordingly Deionized water and ultrasonic device were cleaned, the ultrasonic time was 20min, and it was used after drying;

(2) Preparation of frosting liquid: mixed solution of Na ₂ SiF ₆ , H ₂ C ₂ O ₄ , NH ₄ F, NH ₄ HF ₂ , (NH ₄ ) ₂ SO ₄ , CaF ₂ , KF and K ₂ SO ₄ The salt is dissolved in deionized water and stirred evenly to obtain liquid B; in terms of mass percentage, the composition of liquid B is: 2%-7% Na ₂ SiF ₆ , 2%-3% H ₂ C ₂ O ₄ , 69% -73% NH4F, ₄ %-5% NH4HF2, ₂ %-3% ( _NH4 ) _2SO4 , ₇ %-8% _CaF2 , ₄ %-5% KF, 2%-3% K ₂ SO ₄ , the remainder deionized water; using H ₂ SO ₄ (concentration 35%), adjust the pH value of the liquid B prepared in step (3) to 2.5-7, and the aging environment temperature is 20 ℃-30℃, the aging time is 6-8h, and the frosting liquid is obtained.

(3) Frosting etching: after the single-sided waterproofing treatment of the glass after cleaning in step (1), it is placed in the frosting liquid obtained in step (2) for single-sided frosting, and the frosting time is 3-30 minutes to form on the glass surface. Concave-convex rough structure; rinse the glass surface with a large amount of clean water after etching to remove the particles generated on the glass surface, and sequentially use deionized water and an ultrasonic device for cleaning to obtain frosted glass;

(4) Surface modification: The surface modifier 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane (FDTES) was used to prepare liquid C with methanol as solvent, and the mass concentration of FDTES in liquid C was 2-10% , put the frosted glass in liquid C for 8-10h, and the reaction temperature is 60-65℃; put the glass obtained by the reaction in liquid C at 120-150℃ and heat for 1-2h, clean and dry after cooling to obtain Superhydrophobic antireflection antireflection frosted glass.

Example 1

A super-hydrophobic high-transmission anti-reflection frosted glass, the preparation method comprising the following steps:

(1) Prepare solution A with singalite reagent and deionized water in a molar ratio of 1:1; put the glass substrate in solution A for 10 minutes, and use deionized water and an ultrasonic device for cleaning treatment. The ultrasonic time is 20 minutes, and the drying process is carried out. backup;

(2) Dissolve mixed dissolved salts such as Na ₂ SiF ₆ , H ₂ C ₂ O ₄ , NH ₄ F, NH ₄ HF ₂ , (NH ₄ ) ₂ SO ₄ , CaF ₂ , KF, K ₂ SO ₄ in deionized In water, stir evenly to obtain liquid B; the mass percentages of components in liquid B are: 2% Na ₂ SiF ₆ , 2% H ₂ C ₂ O ₄ , 69% NH ₄ F, 4% NH ₄ HF ₂ , 2% ( NH ₄ ) ₂ SO ₄ , 7% CaF ₂ , 4% KF, 2% K ₂ SO ₄ ; the pH value was adjusted to 2.5 with H ₂ SO ₄ (concentration of 35%), the curing ambient temperature was 20°C, and the curing time is 6h;

(3) The cleaned glass is veneered and placed in liquid B for single-sided frosting. The frosting time is 3 minutes to form a rough structure on the glass surface; after etching, rinse the glass surface with a large amount of water to remove the surface generated The particles are cleaned with deionized water and an ultrasonic device in turn;

(4) The mass concentration of the surface modifier FDTES is 2%, and methanol is used as a solvent to prepare liquid C, and the frosted glass is put into liquid C to react for 8 hours, and the reaction temperature is 60 ° C; the glass obtained by the reaction is placed at 120 ° C. Heating for 1 hour, and then cleaning and drying after cooling.

Example 2

A super-hydrophobic high-transmission anti-reflection frosted glass, the preparation method comprising the following steps:

(1) Prepare solution A with singalite reagent and deionized water in a molar ratio of 1:1; put the glass substrate in solution A for 15 minutes, stir in the film removal solution for 23 minutes, and use deionized water and ultrasonic device in turn for cleaning treatment , the ultrasonic time is 20min, and it is used after drying;

(2) Dissolve mixed dissolved salts such as Na ₂ SiF ₆ , H ₂ C ₂ O ₄ , NH ₄ F, NH ₄ HF ₂ , (NH ₄ ) ₂ SO ₄ , CaF ₂ , KF, K ₂ SO ₄ in deionized In water, stir evenly to obtain liquid B; the mass percentages of components in liquid B are: 3% Na2SiF ₆ , 2.2% H ₂ C ₂ O ₄ , 70% NH ₄ F, 4.3% NH ₄ HF ₂ , 2.5% (NH _{4 )} ) ₂ SO ₄ , 7.2% CaF ₂ , 4.3% KF, 2.2% K ₂ SO ₄ ; use H ₂ SO ₄ (35% concentration) to adjust the pH to 3, the curing ambient temperature is 23°C, and the curing time is 6.5 h;

(3) The cleaned glass is veneered and placed in liquid B for single-sided frosting. The frosting time is 7 minutes to form a rough structure on the glass surface; after etching, rinse the glass surface with a large amount of water to remove the surface generated The particles are cleaned with deionized water and an ultrasonic device in turn;

(4) The mass concentration of the surface modifier FDTES is 4%, and methanol is used as a solvent to prepare liquid C, and the frosted glass is put into liquid C to react for 8.5 hours, and the reaction temperature is 62 ° C; the glass obtained by the reaction is placed at 125 ° C. Heating for 1.2h, and cleaning and drying after cooling.

Example 3

A super-hydrophobic high-transmission anti-reflection frosted glass, the preparation method comprising the following steps:

(1) Prepare solution A with singalite reagent and deionized water in a molar ratio of 1:1; place the glass substrate in solution A for 20 minutes, stir in the film removal solution for 25 minutes, and use deionized water and an ultrasonic device in turn for cleaning treatment , the ultrasonic time is 20min, and it is used after drying;

(2) Dissolve mixed dissolved salts such as Na ₂ SiF ₆ , H ₂ C ₂ O ₄ , NH ₄ F, NH ₄ HF ₂ , (NH ₄ ) ₂ SO ₄ , CaF ₂ , KF, K ₂ SO ₄ in deionized In water, stir evenly to obtain liquid B; the mass percentages of components in liquid B are: 5% Na ₂ SiF ₆ , 2.5% H ₂ C ₂ O ₄ , 71% NH ₄ F, 4.5% NH ₄ HF ₂ , 2.7% ( NH ₄ ) ₂ SO ₄ , 7.5% CaF ₂ , 4.5% KF, 2.5% K ₂ SO ₄ ; use H ₂ SO ₄ (35% concentration) to adjust the pH value to 4, the curing ambient temperature is 25°C, and the curing time is 7h;

(3) The cleaned glass is veneered, placed in liquid B for single-sided frosting, and the frosting time is 10 minutes to form a rough structure on the glass surface; after etching, rinse the glass surface with a large amount of water to remove the surface generated The particles are cleaned with deionized water and an ultrasonic device in turn;

(4) The mass concentration of the surface modifier FDTES is 6%, and methanol is used as a solvent to prepare liquid C, and the frosted glass is put into liquid C to react for 9 hours, and the reaction temperature is 65 ° C; the glass obtained by the reaction is placed at 130 ° C. Heating for 1.5h, cleaning and drying after cooling.

Example 4

A super-hydrophobic high-transmission anti-reflection frosted glass, the preparation method comprising the following steps:

(1) Prepare solution A with the singalite reagent and deionized water in a molar ratio of 1:1; place the glass substrate in solution A for 25 minutes, stir in the film removal solution for 27 minutes, and use deionized water and an ultrasonic device in turn for cleaning treatment , the ultrasonic time is 20min, and it is used after drying;

(2) Dissolve mixed dissolved salts such as Na ₂ SiF ₆ , H ₂ C ₂ O ₄ , NH ₄ F, NH ₄ HF ₂ , (NH ₄ ) ₂ SO ₄ , CaF ₂ , KF, K ₂ SO ₄ in deionized In water, stir evenly to obtain liquid B; the mass percentages of components in liquid B are: 6% Na ₂ SiF ₆ , 2.7% H ₂ C ₂ O ₄ , 72% NH ₄ F, 4.7% NH ₄ HF ₂ , 2.9% ( NH ₄ ) ₂ SO ₄ , 7.8% CaF ₂ , 4.7% KF, 2.7% K ₂ SO ₄ ; use H ₂ SO ₄ (35% concentration) to adjust the pH to 5, the curing ambient temperature is 27°C, and the curing time is 7.5h;

(3) The cleaned glass is veneered, placed in liquid B for single-sided frosting, and the frosting time is 15 minutes to form a rough structure on the glass surface; after etching, rinse the glass surface with a large amount of water to remove the surface generated The particles are cleaned with deionized water and an ultrasonic device in turn;

(4) The mass concentration of surface modifier FDTES is 8%, and methanol is used as solvent to prepare liquid C, and the frosted glass is put into liquid C for reaction for 9.5 hours, and the reaction temperature is 68 °C; the glass obtained by the reaction is placed at 140 °C Heating for 1.7h, and cleaning and drying after cooling.

Example 5

A super-hydrophobic high-transmission anti-reflection frosted glass, the preparation method comprising the following steps:

(1) Prepare solution A with singalite reagent and deionized water in a molar ratio of 1:1; place the glass substrate in solution A for 30 minutes, stir in the film removal solution for 30 minutes, and use deionized water and an ultrasonic device in turn for cleaning treatment , the ultrasonic time is 20min, and it is used after drying;

(2) Dissolve mixed dissolved salts such as Na ₂ SiF ₆ , H ₂ C ₂ O ₄ , NH ₄ F, NH ₄ HF ₂ , (NH ₄ ) ₂ SO ₄ , CaF ₂ , KF, K ₂ SO ₄ in deionized In water, stir evenly to obtain liquid B; the mass percentages of components in liquid B are: 7% Na ₂ SiF ₆ , 3% H ₂ C ₂ O ₄ , 73% NH ₄ F, 5% NH ₄ HF ₂ , 3% ( NH ₄ ) ₂ SO ₄ , 8% CaF ₂ , 5% KF, 3% K ₂ SO ₄ ; the pH value was adjusted to 7 with H ₂ SO ₄ (concentration of 35%), the ambient temperature for curing was 30°C, and the curing time is 8h;

(3) The cleaned glass is veneered, placed in liquid B for single-sided frosting, and the frosting time is 30 minutes to form a rough structure on the glass surface; after etching, rinse the glass surface with a large amount of water to remove the surface generated The particles are cleaned with deionized water and an ultrasonic device in turn;

(4) The mass concentration of the surface modifier FDTES is 10%, and methanol is used as a solvent to prepare liquid C, and the frosted glass is put into liquid C to react for 10 hours, and the reaction temperature is 70 ° C; the glass obtained by the reaction is placed at 150 ° C. Heating for 2h, and cleaning and drying after cooling.

Example 6

A super-hydrophobic high-transmission anti-reflection frosted glass, the preparation method comprising the following steps:

(1) Prepare solution A with the singalite reagent and deionized water in a molar ratio of 1:1; place the glass substrate in solution A for 10 minutes, stir in the film removal solution for 20 minutes, and use deionized water and an ultrasonic device in turn for cleaning treatment , the ultrasonic time is 20min, and it is used after drying;

(2) Dissolve mixed dissolved salts such as Na ₂ SiF ₆ , H ₂ C ₂ O ₄ , NH ₄ F, NH ₄ HF ₂ , (NH ₄ ) ₂ SO ₄ , CaF ₂ , KF, K ₂ SO ₄ in deionized In water, stir evenly to obtain liquid B; the mass percentages of components in liquid B are: 2% Na ₂ SiF ₆ , 2% H ₂ C ₂ O ₄ , 69% NH ₄ F, 4% NH ₄ HF ₂ , 2.2% ( NH ₄ ) ₂ SO ₄ , 7% CaF ₂ , 4% KF, 2% K ₂ SO ₄ ; use H ₂ SO ₄ (concentration of 35%) to adjust the pH value to 3, the curing ambient temperature is 25°C, and the curing time is 6h;

(3) The cleaned glass is veneered and placed in liquid B for single-sided frosting. The frosting time is 3 minutes to form a rough structure on the glass surface; after etching, rinse the glass surface with a large amount of water to remove the surface generated The particles are cleaned with deionized water and an ultrasonic device in turn;

(4) The mass concentration of the surface modifier FDTES is 2%, and methanol is used as a solvent to prepare liquid C, and the frosted glass is put into liquid C to react for 8 hours, and the reaction temperature is 70 ° C; the glass obtained by the reaction is placed at 150 ° C. Heating for 2h, and cleaning and drying after cooling.

Fig. 1 is a SEM image of the surface of the superhydrophobic, antireflection, and antireflection frosted glass prepared in Example 1. It can be seen that the glass has a rough morphology with a lower surface energy. Figure 2 is the contact angle diagram of the superhydrophobic antireflection and antireflection frosted glass surface prepared in Example 1 and the water droplet, the contact angle is 127°, and has a certain hydrophobic ability. FIG. 3 shows the light transmittance of the superhydrophobic, antireflection, antireflection frosted glass prepared in Example 1, and the size is 90%, which is basically close to the light transmittance of ordinary glass. Figure 4 shows the absorbance of the superhydrophobic antireflection and antireflection frosted glass prepared in Example 1, which is about 0.04. Compared with ordinary glass, the absorption capacity of light is significantly improved to achieve the purpose of antireflection.

The invention adopts more environmentally friendly and effective raw material formulations and processes, provides a method for preparing superhydrophobic, antireflection, antireflection frosted glass, improves the light transmittance and hydrophobicity of the frosted glass, and lays a foundation for the practical application of the dual-function glass .

Claims (8)

1, preparation methods of super-hydrophobic anti-reflection frosted glass, which is characterized by comprising the following steps:

(1) preparing a frosting solution: mixing Na₂SiF₆、H₂C₂O₄、NH₄F、NH₄HF₂、(NH₄)₂SO₄、CaF₂KF and K₂SO₄Dissolving the mixed dissolved salt in water, and uniformly stirring to obtain a solution B; adjusting the pH value of the solution B to 2.5-7, and curing to obtain a frosting solution;

(2) frosting and etching: placing the glass into frosting liquid to be frosted on the single surface after the single surface of the glass is subjected to water-proof treatment, and then cleaning the surface of the glass to obtain frosted glass;

(3) surface modification: preparing a surface modifier 1H,1H,2H, 2H-perfluorodecyl triethoxysilane into solution C by using methanol as a solvent, and putting frosted glass into the solution C to react for 8-10H at the temperature of 60-65 ℃; then, the frosted glass is placed in liquid C with the temperature of 120-150 ℃ to be heated for 1-2h, and after cooling, cleaning and drying are carried out, so that the super-hydrophobic anti-reflection frosted glass is obtained.

2. The preparation method of the superhydrophobic antireflection frosted glass according to claim 1, wherein in the step (1), the liquid B comprises the following components in percentage by mass: 2% -7% of Na₂SiF₆2% -3% of H₂C₂O₄69% -73% NH₄F, 4% -5% of NH₄HF₂2% -3% of (NH)₄)₂SO₄7% -8% of CaF₂4% -5% of KF and 2% -3% of K₂SO₄And the balance of deionized water.

3. The method for preparing the super-hydrophobic anti-reflection frosted glass according to claim 1, wherein in the step (1), H is utilized₂SO₄Adjusting the pH value of the solution B to 2.5-7.

4. The method for preparing the super-hydrophobic anti-reflection frosted glass according to claim 1, wherein in the step (1), the curing temperature is 20-30 ℃ and the curing time is 6-8 h.

5. The method for preparing the superhydrophobic antireflection frosted glass according to claim 1, wherein the step (2) is preceded by a glass cleaning step: preparing a solution A from a benzalkonium bromide reagent and water; standing the glass in the solution A for 10-30min, stirring in the membrane removing solution for 20-30min, cleaning with water and ultrasonic device, and drying.

6. The method for preparing the superhydrophobic antireflection frosted glass according to claim 1, wherein in the step (2), the frosting time is 3-30 min.

7. The method for preparing the superhydrophobic antireflection frosted glass according to claim 1, wherein in the step (3), the mass concentration of 1H,1H,2H, 2H-perfluorodecyl triethoxysilane in the solution C is 2-10%.

8. Super-hydrophobic anti-reflection frosted glass obtained by the preparation method of any claim of claims 1-7.

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