CN117417129A - Preparation method of super-hydrophobic glass - Google Patents

Preparation method of super-hydrophobic glass Download PDF

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Publication number
CN117417129A
CN117417129A CN202311350616.7A CN202311350616A CN117417129A CN 117417129 A CN117417129 A CN 117417129A CN 202311350616 A CN202311350616 A CN 202311350616A CN 117417129 A CN117417129 A CN 117417129A
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glass
placing
temperature
solution
particles
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Inventor
彭寿
孙晨蕊
杨勇
曹欣
石丽芬
仲召进
高强
王巍巍
赵凤阳
柯震坤
韩娜
崔介东
单传丽
倪嘉
王鹏
张晓雨
李常青
胡文涛
周刚
李金威
王萍萍
滕飞
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China National Building Material Group Co Ltd CNBM
China Building Materials Glass New Materials Research Institute Group Co Ltd
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China National Building Material Group Co Ltd CNBM
China Building Materials Glass New Materials Research Institute Group Co Ltd
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Priority to CN202311350616.7A priority Critical patent/CN117417129A/en
Publication of CN117417129A publication Critical patent/CN117417129A/en
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • 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
    • C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
    • 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
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • 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
    • C03C2217/21—Oxides
    • 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
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/112—Deposition methods from solutions or suspensions by spraying

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

The invention relates to a preparation method of super-hydrophobic glass, which is characterized by comprising two processes of surface roughening and surface treatment of the glass. Chemical etching and nano SiO 2 The technical route of particle suspension spraying is to construct a micro-nano structure coating on the surface of glass, and the coating has super-hydrophobic performance after further fluorination. The invention adopts chemical etching liquid to carry out chemical etching treatment on the surface of soda-lime-silica glass to obtain the glass surface with different coarse structures, and nano SiO is sprayed on the treated surface 2 Coating layer to make the glass surface rigid micron-level coarse structure constructed by chemical etching and spray-coated nano-level SiO 2 The structures formed by stacking particles on the surface of the glass are mutually staggered,the coating is endowed with good wear resistance.

Description

Preparation method of super-hydrophobic glass
Technical Field
The invention relates to a glass surface treatment process, in particular to a preparation method of super-hydrophobic glass.
Background
The hydrophobic coating has good self-cleaning, waterproof and hygroscopic properties due to the special non-wettability, and is widely applied to the fields of coating, lubrication, waterproof and the like. The super-hydrophobic coating has wide application prospects in various fields in life, such as the fields of being applied to packaging glass of a solar cell panel, preventing glass surface from fogging in winter, self-cleaning automobile windshields and the like.
However, the application of the super-hydrophobic coating in real life is still relatively difficult, and the preparation of the super-hydrophobic coating on the glass surface and the application thereof in life still have the problems of long preparation time, complex preparation process, poor stability, poor mechanical properties and the like.
Disclosure of Invention
To solve the problems, the invention aims to provide a preparation method of super-hydrophobic glass, which comprises the steps of mixing nano SiO with different agglomeration degrees 2 And (3) spraying the particle suspension on the etched glass surface to obtain a coating, and carrying out heat treatment and PFTS fluorination on the coating to obtain the superhydrophobic coating.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the super-hydrophobic glass is characterized by comprising the following steps of:
1) Horizontally placing the glass sample in a container containing etching liquid, placing the container in a constant-temperature water bath, controlling the temperature of the etching liquid to be 25-85 ℃ and the etching time to be 30-80 min, taking out the glass sample, and washing and drying the glass sample with deionized water;
2) The etched surface of the glass is used as a substrate,with arranged nano SiO 2 Spraying the ethanol solution of the particles on the surface of the glass to form a film, and then placing a glass sample into a high-temperature furnace for heat treatment;
3) Placing the heat-treated glass sample into a normal hexane solution containing perfluorodecyl triethoxysilane for reaction treatment for 1-3 min, and performing nano SiO (silicon dioxide) 2 And modifying the particles, and performing heat treatment to obtain the super-hydrophobic coating.
On the basis of the technical scheme, the following further technical scheme is provided:
the etching liquid consists of the following raw materials in percentage by mass: ammonium sulfate: oxalic acid: water=10 to 15: 2.5-3:5-9.5: 95-100.
The nano SiO 2 The preparation of the particles comprises the following steps:
to 4 mL of 25% NH 3 •H 2 O and 80 mL of 95% C 2 H 5 Adding 0.15 g-0.35 g of cetyltrimethylammonium bromide (CTAB) into a beaker of the mixed solution of OH, putting the mixed solution into a constant-temperature magnetic stirrer, uniformly mixing, and taking out the mixed solution of CTAB when the CTAB is completely dissolved;
dripping 2 mL tetraethoxysilane TEOS into 80 mL of 95% C 2 H 5 In a beaker of OH solution;
TEOS and C 2 H 5 Pouring the mixed solution of OH into a beaker of the CTAB mixed solution prepared before, stirring uniformly by a magnetic stirrer, reacting at 40 ℃ for 12 h, placing the beaker containing the reaction solution into a drying box for drying after the reaction is finished, and finally obtaining the nano SiO with different agglomeration degrees 2 The particles are obtained to obtain SiO with different particle size distribution 2 And (3) particles.
The nano SiO 2 The ethanol solution of the particles is sprayed on the surface of the glass to form a film, and the method comprises the following steps: 0.15 g-0.35 g of nano SiO with different agglomeration degrees is taken 2 Placing the particles into a beaker, and respectively adding 30-40 mL of 95% C 2 H 5 Placing the nano SiO into an OH solution, and stirring the solution in an ultrasonic cleaner for 25-35 min to obtain the nano SiO 2 Spraying liquid on particles;
nano SiO 2 Spraying the particle spraying liquid to the etched partPlacing the glass sample on the etched surface of the glass sample, after spraying, placing the glass sample in a high-temperature furnace, performing heat treatment at 300-550 ℃ for 30-60 min, taking out and naturally cooling;
and then, placing the glass sample into a normal hexane solution of perfluorodecyl triethoxysilane PFTS with the mass concentration of 2% to react for 1-3 min, naturally airing, then placing the glass sample into a high Wen Luzhong temperature of 400-430 ℃ to keep the temperature for 3-5 min, taking out, and cooling to room temperature.
The invention has the beneficial effects that nano SiO is accumulated on the surface of the chemically etched glass 2 The particles achieve the purpose of superhydrophobicity. Nano SiO 2 The particles have a number of specific properties, such as improved ageing resistance, strength, uv resistance and chemical resistance of other materials and a wide range of applications.
Drawings
FIG. 1 is a plot of the number of rubs on sandpaper versus the water contact angle for the coating prepared in example 1;
FIG. 2 is NH in example 2 4 F, a relation diagram of the addition amount, roughness and transmittance;
FIG. 3 is the sample (NH) in example 2 4 ) 2 SO 4 A relation chart of the addition amount, the roughness and the transmittance;
FIG. 4 is C in example 2 2 H 2 O 4 •2H 2 A graph of the relationship between the O addition and the roughness and transmittance;
FIG. 5 is H in example 2 2 A graph of the relationship between the O addition and the roughness and transmittance;
FIG. 6 example 3 effect of etch temperature on glass roughness and transmittance;
FIG. 7 example 4 effect of etch time on glass roughness and transmittance;
FIG. 8 is a plot of the number of rubs on sandpaper versus the water contact angle for the coating of comparative example 1;
FIG. 9 is a plot of the number of rubs on sandpaper versus the water contact angle for the coating produced in comparative example 2.
Description of the embodiments
The present invention is described in further detail below by way of the following detailed description, which is presented herein for purposes of illustration and explanation only and is not intended to be limiting.
Examples
Preparation method of super-hydrophobic glass according to NH 4 F:(NH 4 ) 2 SO 4 :C 2 H 2 O 4 •2H 2 O: H 2 O=10:2.5:9.5:95 etching solution was prepared, and after placing on a constant temperature magnetic stirrer and stirring sufficiently, it was allowed to stand at room temperature for 12 h. And horizontally placing the glass in the prepared etching liquid, attaching a protective film on the surface of the glass which is not required to be etched, accurately controlling the temperature of the etching liquid in an electronic constant-temperature water bath kettle to 75 ℃, and keeping the temperature for 50 minutes. After the reaction was completed, the sample was taken out, washed with deionized water and dried.
To 4 mL of 25% NH 3 •H 2 O and 80 mL of 95% C 2 H 5 A certain amount of cetyltrimethylammonium bromide (CTAB) is added into the mixed solution of OH, the mixed solution is put into a constant temperature magnetic stirrer to be uniformly mixed, and the mixed solution is taken out when CTAB is completely dissolved. A further drop of 2 mL tetraethyl orthosilicate (TEOS) was applied using a dropper to 80 mL of 95% C 2 H 5 In a beaker of OH solution. TEOS and C 2 H 5 The OH mixed solution was quickly poured into a beaker of the CTAB mixed solution previously prepared and stirred well with a magnetic stirrer and reacted at a temperature of 40℃for 12 h. After the reaction is finished, placing the beaker solution with the complete reaction in a drying oven for drying to finally obtain nano SiO with different agglomeration degrees 2 The particles are obtained to obtain SiO with different particle size distribution 2 And (3) particles.
0.3g of nano SiO with different agglomeration degree is taken 2 The pellets were placed in beakers and 35 mL of 95% C was added, respectively 2 H 5 Placing the mixture into an ultrasonic cleaner, and stirring for 30 min. Ultrasonic dispersion of nano SiO with a spray pen 2 The particles are sprayed onto the etched glass surface. After the spraying was completed, the glass sample was placed in a high temperature furnace and heat treated at 550 ℃ for 1 h. Cooling, placing the treated glass sheet into 2% n-hexane solution of 1H, 2H-perfluorodecyl triethoxysilane (PFTS) for reaction for 1 min, naturally air-drying for 30 min, and then placing into a 420 deg.C high temperature furnace for heat preservation for 3 min, collectingAfter the reaction, the mixture was cooled to room temperature.
There are many methods for testing the abrasion resistance of superhydrophobic coatings, such as friction test, sand impact test, pencil hardness test, tape test, etc., and the patent finally adopts sand paper friction test experiment. The sample was loaded with a 100 g weight and abraded on 600 mesh sandpaper to test the relationship between the number of rubs and the water contact angle, as shown in fig. 1, the coating had a 167.34 ° contact angle before abrasion, and the contact angle was changed after 50 sandpaper rubbing cycle tests, but remained substantially above 156 °, which indicated that the coating remained well superhydrophobic and significantly improved its abrasion resistance.
Example 2 (changing etching solution ratio)
Preparation method of super-hydrophobic glass according to NH 4 F:(NH 4 ) 2 SO 4 :C 2 H 2 O 4 •2H 2 O: H 2 O=15:3:5:100 etching solution was placed on a constant temperature magnetic stirrer and stirred well, and then left to stand at room temperature for 12 h. And horizontally placing the glass in the prepared etching liquid, attaching a protective film on the surface of the glass which is not required to be etched, accurately controlling the temperature of the etching liquid in an electronic constant-temperature water bath kettle to 75 ℃, and keeping the temperature for 50 minutes. After the reaction was completed, the sample was taken out, washed with deionized water and dried.
To 4 mL of 25% NH 3 •H 2 O and 80 mL of 95% C 2 A certain amount of cetyltrimethylammonium bromide (CTAB) is added into the mixed solution of H5OH, the mixture is put into a constant temperature magnetic stirrer to be uniformly mixed, and the mixture is taken out when the CTAB is completely dissolved. A further drop of 2 mL tetraethyl orthosilicate (TEOS) was applied using a dropper to 80 mL of 95% C 2 H 5 In a beaker of OH solution. TEOS and C 2 H 5 The OH mixed solution was quickly poured into a beaker of the CTAB mixed solution previously prepared and stirred well with a magnetic stirrer and reacted at a temperature of 40℃for 12 h. After the reaction is finished, placing the beaker solution with the complete reaction in a drying oven for drying to finally obtain nano SiO with different agglomeration degrees 2 The particles are obtained to obtain SiO with different particle size distribution 2 And (3) particles.
0.3g of different materials is takenAgglomeration degree nano SiO 2 The pellets were placed in beakers and 35 mL of 95% C was added, respectively 2 H 5 Placing the mixture into an ultrasonic cleaner, and stirring for 30 min. Ultrasonic dispersion of nano SiO with a spray pen 2 The particles are sprayed onto the etched glass surface. After the spraying was completed, the glass sample was placed in a high temperature furnace and heat treated at 550 ℃ for 1 h. After cooling, the treated glass sheet is put into 1H, 2H-perfluoro decyl triethoxysilane (PFTS) n-hexane solution with mass concentration of 2% to react for 1 min, naturally air-dried for 30 min, then put into a temperature of Wen Luzhong with the temperature of 420 ℃ to be kept for 3 min, taken out and cooled to room temperature.
And determining the components of various chemical components by a single factor experiment based on the transmittance and roughness data, and researching the correlation between the microstructure of the glass surface and the preparation process and the optical performance of the glass. As can be seen from FIG. 2, with NH in the etching solution 4 The adding amount of F is gradually increased, and the roughness and the transmittance of the glass are gradually increased and then reduced; when NH 4 When the addition amount of F was 10 g, the maximum value of the roughness and transmittance of the glass appeared. And then continuously adding NH 4 F, roughness and transmittance are reduced.
As shown in fig. 3, the roughness and transmittance of the glass are a function of (NH 4 ) 2 SO 4 The increase of the adding amount shows a more complex development trend; when (NH) 4 ) 2 SO 4 When the addition amount is 3g, the transmittance is maximum, but the roughness is smaller at this time; when (NH) 4 ) 2 SO 4 When the amount of the additive was 4 g, the roughness was maximum, but the transmittance was small. While when (NH) 4 ) 2 SO 4 When the addition amount is 2 g, the roughness and transmittance are both large, and (NH) 4 ) 2 SO 4 As a dispersing agent, the viscosity of the etching liquid formula can be adjusted, and the dispersing agent can also be used as the dispersing agent of the etching liquid. It has good etching effect, but the addition amount is not excessive, the excessive amount can reduce the concentration of the effective components, and the excessive NH4 + Will bind to HF, thereby reducing the concentration of HF, so (NH) 4 ) 2 SO 4 The amount of (2) should not be excessively large. To sum up, (NH) 4 ) 2 SO 4 Preliminary selection of the addition amount of (2)2 g.
As shown in FIG. 4, C 2 H 2 O 4 •2H 2 The influence curve of the addition amount of O on the roughness and the transmittance is in a trend of decreasing first and then increasing then decreasing, C 2 H 2 O 4 •2H 2 When the O dosage reaches 9 g, the transmittance and roughness of the sample are along with C 2 H 2 O 4 •2H 2 The amount of O decreases with increasing amount of O. This is probably due to C 2 H 2 O 4 •2H 2 O increases H in the etching solution + In an amount and ionized with fluoride F - To indirectly produce HF for etching glass, but adding excessive C 2 H 2 O 4 •2H 2 O can cause uneven corrosion and reduce the roughness and transmittance of the glass.
It can be seen from FIG. 5 that as H follows 2 The increase in the amount of O tends to increase and decrease the overall roughness and transmittance. The roughness reaches the maximum value at 95 g, and the transmittance is larger at the moment; the transmittance reaches a maximum at 100 g, and the roughness is also large. Comprehensively consider, preliminarily select H 2 The addition amount of O was 100 g.
Example 3 (changing etching temperature)
Preparation method of super-hydrophobic glass according to NH 4 F:(NH 4 ) 2 SO 4 :C 2 H 2 O 4 •2H 2 O: H 2 O=10:2.5:9.5:95 etching solution was prepared, and after placing on a constant temperature magnetic stirrer and stirring sufficiently, it was allowed to stand at room temperature for 12 h. And horizontally placing the glass in the prepared etching liquid, attaching a protective film on the surface of the glass which is not required to be etched, accurately controlling the temperature of the etching liquid in an electronic constant-temperature water bath kettle to be 50 ℃, and keeping the temperature for 50 minutes. After the reaction was completed, the sample was taken out, washed with deionized water and dried.
To 4 mL of 25% NH 3 •H 2 O and 80 mL of 95% C 2 H 5 A certain amount of cetyltrimethylammonium bromide (CTAB) is added into the mixed solution of OH, the mixed solution is put into a constant temperature magnetic stirrer to be uniformly mixed, and the mixed solution is taken out when CTAB is completely dissolved. In addition to using droppersDripping 2 mL Tetraethoxysilane (TEOS) into 80 mL of 95% C 2 H 5 In a beaker of OH solution. TEOS and C 2 H 5 The OH mixed solution was quickly poured into a beaker of the CTAB mixed solution previously prepared and stirred well with a magnetic stirrer and reacted at a temperature of 40℃for 12 h. After the reaction is finished, placing the beaker solution with the complete reaction in a drying oven for drying to finally obtain nano SiO with different agglomeration degrees 2 The particles are obtained to obtain SiO with different particle size distribution 2 And (3) particles.
0.3g of nano SiO with different agglomeration degree is taken 2 The pellets were placed in beakers and 35 mL of 95% C was added, respectively 2 H 5 Placing the mixture into an ultrasonic cleaner, and stirring for 30 min. Ultrasonic dispersion of nano SiO with a spray pen 2 The particles are sprayed onto the etched glass surface. After the spraying was completed, the glass sample was placed in a high temperature furnace and heat treated at 550 ℃ for 1 h. After cooling, the treated glass sheet is put into 1H, 2H-perfluoro decyl triethoxysilane (PFTS) n-hexane solution with mass concentration of 2% to react for 1 min, naturally air-dried for 30 min, then put into a temperature of Wen Luzhong with the temperature of 420 ℃ to be kept for 3 min, taken out and cooled to room temperature.
The optimum etching temperature of the glass in the etching process is explored by using the transmittance and roughness data, and as can be seen from fig. 6, under the condition of a certain etching time, the roughness of the glass gradually increases when the temperature is continuously increased. And the transmittance of the glass increases and then decreases with increasing temperature. At a temperature of 75 ℃, the transmittance of the glass is the highest. This occurs because the temperature increases to increase the reactivity of the reactants and the etch rate gradually increases. When the chemical etching temperature is 75 ℃, the microparticles are uniformly distributed on the etched glass surface and show better surface morphology, and the transmittance reaches the highest. When the temperature is continuously increased, the microparticles on the surface of the glass can be dissolved due to high temperature, so that the surface morphology of the glass can be damaged, the capture of light by the rough structure on the surface of the glass is reduced, and the transmittance of the etched glass is reduced. Thus, the etching temperature of the glass was controlled at 75 ℃.
Example 4 (changing etching time)
Preparation method of super-hydrophobic glass according to NH 4 F:(NH 4 ) 2 SO 4 :C 2 H 2 O 4 •2H 2 O: H 2 O=10:2.5:9.5:95 etching solution was prepared, and after placing on a constant temperature magnetic stirrer and stirring sufficiently, it was allowed to stand at room temperature for 12 h. And horizontally placing the glass in the prepared etching solution, attaching a protective film on the surface of the glass which is not required to be etched, accurately controlling the temperature of the etching solution in an electronic constant-temperature water bath kettle to 75 ℃, and keeping the temperature for 30 minutes. After the reaction was completed, the sample was taken out, washed with deionized water and dried.
To 4 mL of 25% NH 3 •H 2 O and 80 mL of 95% C 2 H 5 A certain amount of cetyltrimethylammonium bromide (CTAB) is added into the mixed solution of OH, the mixed solution is put into a constant temperature magnetic stirrer to be uniformly mixed, and the mixed solution is taken out when CTAB is completely dissolved. A further drop of 2 mL tetraethyl orthosilicate (TEOS) was applied using a dropper to 80 mL of 95% C 2 H 5 In a beaker of OH solution. TEOS and C 2 H 5 The OH mixed solution was quickly poured into a beaker of the CTAB mixed solution previously prepared and stirred well with a magnetic stirrer and reacted at a temperature of 40℃for 12 h. After the reaction is finished, placing the beaker solution with the complete reaction in a drying oven for drying to finally obtain nano SiO with different agglomeration degrees 2 The particles are obtained to obtain SiO with different particle size distribution 2 And (3) particles.
0.3g of nano SiO with different agglomeration degree is taken 2 The pellets were placed in beakers and 35 mL of 95% C was added, respectively 2 H 5 Placing the mixture into an ultrasonic cleaner, and stirring for 30 min. Ultrasonic dispersion of nano SiO with a spray pen 2 The particles are sprayed onto the etched glass surface. After the spraying was completed, the glass sample was placed in a high temperature furnace and heat treated at 550 ℃ for 1 h. After cooling, the treated glass sheet is put into 1H, 2H-perfluoro decyl triethoxysilane (PFTS) n-hexane solution with mass concentration of 2% to react for 1 min, naturally air-dried for 30 min, then put into a temperature of Wen Luzhong with the temperature of 420 ℃ to be kept for 3 min, taken out and cooled to room temperature.
As shown in fig. 7, the optimum etching time of the glass in the etching process is studied by using the transmittance and roughness data, and it can be seen that the transmittance of the glass increases and decreases reciprocally with the increase of time. When the chemical etching time is 70 min, the transmittance of the glass after etching reaches the maximum value, and when the chemical etching time is 50 min, the transmittance of the glass after etching reaches the second maximum value. However, as the etching reaction proceeds, the transmittance decreases. The reason for this phenomenon is that as the etching reaction proceeds, a fluorosilicate with higher insolubility is produced and deposited on the surface of the glass, preventing the glass from continuing to react with the etching solution, and thus reducing the transmittance of the glass. In order to obtain glass with high transmittance, and control the roughness in a proper range, the preparation efficiency of the glass is improved, and the etching time is selected to be 50 min.
Comparative example 1 (modification of SiO) 2 Method for bonding particles to glass surfaces
Preparation method of super-hydrophobic glass according to NH 4 F:(NH 4 ) 2 SO 4 :C 2 H 2 O 4 •2H 2 O: H 2 O=10:2.5:9.5:95 etching solution was prepared, and after placing on a constant temperature magnetic stirrer and stirring sufficiently, it was allowed to stand at room temperature for 12 h. And horizontally placing the glass in the prepared etching liquid, attaching a protective film on the surface of the glass which is not required to be etched, accurately controlling the temperature of the etching liquid in an electronic constant-temperature water bath kettle to 75 ℃, and keeping the temperature for 50 minutes. After the reaction was completed, the sample was taken out, washed with deionized water and dried.
To 4 mL of 25% NH 3 •H 2 O and 80 mL of 95% C 2 H 5 A certain amount of cetyltrimethylammonium bromide (CTAB) is added into the mixed solution of OH, the mixed solution is put into a constant temperature magnetic stirrer to be uniformly mixed, and the mixed solution is taken out when CTAB is completely dissolved. A further drop of 2 mL tetraethyl orthosilicate (TEOS) was applied using a dropper to 80 mL of 95% C 2 H 5 In a beaker of OH solution. TEOS and C 2 H 5 The OH mixed solution was rapidly poured into a beaker of the CTAB mixed solution previously prepared and stirred uniformly with a magnetic stirrer at a temperature of 40℃Reaction 12 h at room temperature. After the reaction is finished, placing the beaker solution with the complete reaction in a drying oven for drying to finally obtain nano SiO with different agglomeration degrees 2 The particles are obtained to obtain SiO with different particle size distribution 2 And (3) particles.
0.3g of nano SiO with different agglomeration degree is taken 2 The pellets were placed in beakers and 35 mL of 95% C was added, respectively 2 H 5 Placing the mixture into an ultrasonic cleaner, and stirring for 30 min. Immersing the chemically etched glass sample into a solution containing dispersed nano SiO 2 The particles were placed in a beaker (a protective film was also attached to the surface of the glass which was not etched), and the glass was taken out after leaving for a while. The glass sample was placed in a high temperature furnace and heat treated at 550 ℃ for 1 h. After cooling, the treated glass sheet is put into 1H, 2H-perfluoro decyl triethoxysilane (PFTS) n-hexane solution with mass concentration of 2% to react for 1 min, naturally air-dried for 30 min, then put into a temperature of Wen Luzhong with the temperature of 420 ℃ to be kept for 3 min, taken out and cooled to room temperature.
The samples were loaded with 100 g weights and abraded on 600 mesh sandpaper to test the relationship of different numbers of rubs to water contact angle. The contact angle of the coating shown in fig. 8 is 166.06 plus or minus 2 degrees before abrasion, slightly reduced to 164.02 plus or minus 2 degrees after the 1 st abrasion, and the rough structure of the surface of the coating is partially destroyed after 50 times of abrasive paper abrasion test, but the effect is not as good as that of the coating prepared by a spraying method.
Comparative example 2 (changing etching liquid type)
A process for preparing superhydrophobic glass includes such steps as proportionally preparing etching liquid from HF (8%), HCl (5%), stirring by constant-temp magnetic stirrer, and standing at room temp for 12 h. And horizontally placing the glass in the prepared etching liquid, accurately controlling the etching liquid at 75 ℃ in an electronic constant-temperature water bath, and keeping the temperature for 30 minutes. After the reaction was completed, the sample was taken out, washed with deionized water and dried.
To 4 mL NH 3 •H 2 O and 80 mL C 2 H 5 Adding a certain amount of CTAB into the mixed solution of OH, putting into a constant-temperature magnetic stirrer, uniformly mixing, and taking out when CTAB is completely dissolved. Another dropping of 2 mL TEOS into 80 mL C using a dropper 2 H 5 In a beaker of OH solution. TEOS and C 2 H 5 The OH mixed solution was quickly poured into a beaker of the CTAB mixed solution previously prepared and stirred well with a magnetic stirrer and reacted at a temperature of 40℃for 12 h. After the reaction is finished, placing the beaker solution with the complete reaction in a drying oven for drying to finally obtain nano SiO with different agglomeration degrees 2 And (3) particles.
Taking nano SiO with different agglomeration degrees 2 The pellets were placed in beakers and 35 mL of C were added separately 2 H 5 Placing the mixture into an ultrasonic cleaner, and stirring for 30 min. Ultrasonic dispersion of nano SiO with a spray pen 2 The particles are sprayed onto the etched glass surface. After the spraying was completed, the glass sample was placed in a high temperature furnace and heat treated at 550 ℃ for 1 h. Cooling, placing the treated glass sheet into a normal hexane solution with the mass concentration of 2% PFTS for reaction for 1 min, naturally air-drying for 30 min, then placing the glass sheet into a high Wen Luzhong reactor with the temperature of 420 ℃ for 3 min, taking out, and cooling to room temperature.
The samples were loaded with 100 g weights and abraded on 600 mesh sandpaper to test the relationship of different numbers of rubs to water contact angle. As shown in fig. 9, after 38 rubbing cycles, the water contact angle of the coating which is not etched is lower than 150 degrees, and the superhydrophobic performance is lost.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention in any way; any person skilled in the art can make many possible variations and modifications to the technical solution of the present invention or modifications to equivalent embodiments using the methods and technical contents disclosed above, without departing from the scope of the technical solution of the present invention. Therefore, any simple modification, equivalent substitution, equivalent variation and modification of the above embodiments according to the technical substance of the present invention, which do not depart from the technical solution of the present invention, still fall within the scope of the technical solution of the present invention.

Claims (4)

1. The preparation method of the super-hydrophobic glass is characterized by comprising the following steps of:
1) Horizontally placing the glass sample in a container containing etching liquid, placing the container in a constant-temperature water bath, controlling the temperature of the etching liquid to be 25-85 ℃ and the etching time to be 30-80 min, taking out the glass sample, and washing and drying the glass sample with deionized water;
2) Using glass etched surface as substrate, using nano SiO 2 Spraying the ethanol solution of the particles on the surface of the glass to form a film, and then placing a glass sample into a high-temperature furnace for heat treatment;
3) Placing the heat-treated glass sample into a normal hexane solution containing perfluorodecyl triethoxysilane for reaction treatment for 1-3 min, and performing nano SiO (silicon dioxide) 2 And modifying the particles, and performing heat treatment to obtain the super-hydrophobic coating.
2. The method for preparing the super-hydrophobic glass according to claim 1, wherein the etching solution comprises the following raw materials in percentage by mass: ammonium sulfate: oxalic acid: water=10 to 15: 2.5-3:5-9.5: 95-100.
3. The method for preparing super-hydrophobic glass according to claim 1, wherein nano SiO 2 The preparation of the particles comprises the following steps:
to 4 mL of 25% NH 3 •H 2 O and 80 mL of 95% C 2 H 5 Adding 0.15 g-0.35 g of cetyltrimethylammonium bromide (CTAB) into a beaker of the mixed solution of OH, putting the mixed solution into a constant-temperature magnetic stirrer, uniformly mixing, and taking out the mixed solution of CTAB when the CTAB is completely dissolved;
dripping 2 mL tetraethoxysilane TEOS into 80 mL of 95% C 2 H 5 In a beaker of OH solution;
TEOS and C 2 H 5 Pouring the mixed solution of OH into a beaker of the CTAB mixed solution prepared before, stirring uniformly by a magnetic stirrer, reacting at 40 ℃ for 12 h, placing the beaker containing the reaction solution into a drying box for drying after the reaction is finished, and finally obtaining the nano SiO with different agglomeration degrees 2 The particles are obtained to obtain SiO with different particle size distribution 2 And (3) particles.
4. A method of preparing a superhydrophobic glass according to claim 3, comprising the steps of: 0.15 g-0.35 g of nano SiO with different agglomeration degrees is taken 2 Placing the particles into a beaker, and respectively adding 30-40 mL of 95% C 2 H 5 Placing the nano SiO into an OH solution, and stirring the solution in an ultrasonic cleaner for 25-35 min to obtain the nano SiO 2 Spraying liquid on particles;
nano SiO 2 Spraying the particle spraying liquid onto the etched surface of the etched glass sample, after the spraying, placing the glass sample into a high-temperature furnace, performing heat treatment at 300-550 ℃ for 30-60 min, taking out, and naturally cooling;
and then, placing the glass sample into a normal hexane solution of perfluorodecyl triethoxysilane PFTS with the mass concentration of 2% to react for 1-3 min, naturally airing, then placing the glass sample into a high Wen Luzhong temperature of 400-430 ℃ to keep the temperature for 3-5 min, taking out, and cooling to room temperature.
CN202311350616.7A 2023-10-18 2023-10-18 Preparation method of super-hydrophobic glass Pending CN117417129A (en)

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