CN114105684A - Super-hydrophobic building ceramic tile and preparation method thereof - Google Patents

Super-hydrophobic building ceramic tile and preparation method thereof Download PDF

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Publication number
CN114105684A
CN114105684A CN202111065188.4A CN202111065188A CN114105684A CN 114105684 A CN114105684 A CN 114105684A CN 202111065188 A CN202111065188 A CN 202111065188A CN 114105684 A CN114105684 A CN 114105684A
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coating
ceramic tile
building ceramic
slurry
building
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李润润
闫朝一
李月明
沈宗洋
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Jingdezhen Ceramic Institute
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Jingdezhen Ceramic Institute
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Abstract

The invention discloses a super-hydrophobic building ceramic tile and a preparation method thereof, which are composed of a building ceramic tile green body and a composite coating coated on the surface of the building ceramic tile green body; the composite coating is at least two layers, namely a bottom coating and a surface coating; the raw materials of the building ceramic tile blank body comprise 5-20 wt% of Jiepai soil, 5-25 wt% of Minqing soil, 0-15 wt% of Lian soil, 10-40 wt% of quartz and 20-45 wt% of feldspar; the bottom coating comprises the following raw materials of 10-30 wt% of alumina, 30-60 wt% of quartz, 10-25 wt% of limestone, 10-25 wt% of dolomite, 0-10 wt% of spodumene and 1-10 wt% of zinc oxide; the surface coating is composed of polystyrene slurry with the concentration of 0.01-1 mol/L and a binder. According to the invention, through the formula design and the use of the composite coating, the super-hydrophobic self-cleaning performance of the building ceramic tile is realized; the preparation method has low production cost and simple method, can be widely applied to the production of various building ceramic tiles, and has high practical value and application prospect.

Description

Super-hydrophobic building ceramic tile and preparation method thereof
Technical Field
The invention relates to the technical field of building ceramic materials, in particular to a super-hydrophobic building ceramic tile and a preparation method thereof.
Background
With the progress of science and technology, the living standard of people is continuously improved, the building ceramic tiles are widely applied to various house decorations, and the application range and the using amount of the ceramic tiles are also remarkably increased. For example, the building exterior wall tiles are mainly applied to decoration and protection of building exterior walls due to good acid and alkali resistance and stable physical and chemical properties. Interior wall and floor tiles are also used for interior and exterior finishing because of their smooth, self-cleaning properties. However, for the exterior wall tile, because the exterior wall tile is exposed in the air all the year round, the surface of the exterior wall tile is washed by water, dust or other suspended particles are polluted and adhered to the exterior wall tile, so that the wall is affected with damp and mildewed, the beauty of the building is greatly damaged, and a large amount of manpower and material resources are needed to clean every year. The inner wall tiles and the floor tiles usually have the phenomenon of getting damp, and the floor tiles applied outdoors are easy to freeze in cold winter. Therefore, the prepared ceramic tile with the super-hydrophobic property can keep the wall surface dry, so that the wall surface has excellent waterproof and anti-icing capabilities, and has the characteristics of self-cleaning, corrosion resistance and prevention of mildew caused by the fact that the wall body is wet.
At present, methods for preparing the super-hydrophobic material include a spraying method, an etching method, a sol-gel method and the like. Among them, the spraying method is widely used due to the characteristics of simple process, low cost, suitability for large-area production, and the like. Although the reports on the super-hydrophobic materials are more, the reports on the super-hydrophobic self-cleaning building ceramic tiles are not found yet.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a super-hydrophobic building ceramic tile, which realizes the super-hydrophobic self-cleaning performance of the building ceramic tile through formula design and use of a composite coating. The invention also aims to provide a preparation method of the super-hydrophobic building ceramic tile.
The purpose of the invention is realized by the following technical scheme:
the invention provides a super-hydrophobic building ceramic tile which is composed of a building ceramic tile green body and a composite coating coated on the surface of the building ceramic tile green body; the composite coating is at least two layers, namely a bottom coating and a surface coating; the raw materials of the building ceramic tile blank body comprise 5-20 wt% of Jiepai soil, 5-25 wt% of Minqing soil, 0-15 wt% of Lian soil, 10-40 wt% of quartz and 20-45 wt% of feldspar; the bottom coating comprises the following raw materials of 10-30 wt% of alumina, 30-60 wt% of quartz, 10-25 wt% of limestone, 10-25 wt% of dolomite, 0-10 wt% of spodumene and 1-10 wt% of zinc oxide; the surface coating is composed of polystyrene slurry with the concentration of 0.01-1 mol/L and a binder, wherein the binder is one or a combination of CMC, PVA and fluorinated polyurethane elastomer, and the polystyrene slurry and the binder are in a molar ratio of 1: 0.1-0.4.
Further, the composite coating of the present invention further comprises an intermediate transparent coating layer positioned between the base coating layer and the surface coating layer; the intermediate transparent coating comprises the following raw materials of 10-30 wt% of potash feldspar, 20-50 wt% of quartz, 7-19 wt% of limestone, 3-7 wt% of dolomite, 0-10 wt% of spodumene, 1-9 wt% of zinc oxide and 1-58 wt% of fusion cakes. The frit has a chemical composition of SiO240~60wt%、K2O 1~10wt%、Na2O 1~ 10wt%、CaO 5~10wt%、Al2O36~17wt%、B2O35~17wt%。
The other purpose of the invention is realized by the following technical scheme:
the preparation method of the super-hydrophobic building ceramic tile provided by the invention comprises the following steps:
(1) preparation of building ceramic tile green body
Mixing the raw materials of the building ceramic tile green body uniformly according to a ratio, performing ball milling, sieving, ageing, stirring, refining, grouting, drying and biscuit firing treatment, and cooling to obtain a building ceramic tile green body;
(2) preparation of bottom coating slurry and intermediate transparent coating slurry
Uniformly mixing the raw materials of the bottom coating according to a ratio, and performing ball milling and sieving to obtain uniform bottom coating slurry; preparing intermediate transparent coating slurry by the same method;
(3) preparation of bottom coat, intermediate clear coat
Uniformly coating the bottom coating slurry on the surface of a building ceramic tile green body, and drying in the shade to obtain the building ceramic tile green body with the bottom coating; or continuously coating the intermediate transparent coating slurry on the bottom coating, and drying in the shade to obtain a green body of the architectural ceramic tile with the intermediate transparent coating;
(4) preparation of polystyrene slurry
Mixing potassium hydroxide and a styrene monomer according to the volume ratio of 1: 1, carrying out ultrasonic treatment for 10-60 min, standing, taking upper styrene, and adding a potassium persulfate solution with the concentration of 0.001-0.05 mol/L and a hexadecyl trimethyl ammonium bromide solution with the concentration of 0.001-0.07 mol/L to form a mixed solution; wherein, the volume ratio of the styrene monomer to the potassium persulfate solution to the hexadecyl trimethyl ammonium bromide solution is 1: 0.1-6; placing the mixed solution in a water bath at the temperature of 60-100 ℃, and heating and stirring for 1-50 h; centrifugally cleaning for 2-30 times, and adding water to prepare polystyrene slurry with the concentration of 0.01-1 mol/L;
(5) preparation of surface coating slurries
Uniformly mixing the polystyrene slurry and a binder according to a ratio to obtain surface coating slurry;
(6) preparation of surface coatings
And uniformly spraying the surface coating slurry on a building ceramic tile blank with a bottom coating or a building ceramic tile blank with a middle transparent coating by adopting a spraying method, and drying to obtain the super-hydrophobic building ceramic tile.
Further, in the preparation method, the bisque firing temperature in the step (1) is 600-1300 ℃. The spraying method in the step (6) is as follows: the spraying air pressure is 0.1-5 MPa, the diameter of a nozzle is 1-5 mm, and the distance between the nozzle and the base coat is 1-20 cm; the drying temperature is 80-280 ℃, and the drying time is 1-60 min.
The invention has the following beneficial effects:
(1) the invention forms the building ceramic tile with ultrahigh hydrophobicity and good self-cleaning performance by constructing the composite coating for the first time, and provides a feasible method for preparing the high-performance super-hydrophobic self-cleaning material. The super-hydrophobic self-cleaning building ceramic tile prepared by the invention has a contact angle larger than 155 degrees, can well eliminate dust and other pollution by utilizing rainwater or fog drops, is waterproof and anti-freezing, and has great application potential in the industrial field.
(2) The preparation method has low production cost and simple method, can be widely applied to the production of various building ceramic tiles, and has high practical value and application prospect.
The present invention will be described in further detail with reference to examples.
Detailed Description
The invention provides a super-hydrophobic building ceramic tile which is composed of a building ceramic tile body and a composite coating coated on the surface of the building ceramic tile body. The composite coating is at least two layers, namely a bottom coating and a surface coating; alternatively, an intermediate clear coat layer is included between the base coat layer and the top coat layer.
The raw materials of the building ceramic tile blank comprise 5-20 wt% of Jiepai soil, 5-25 wt% of Minqing soil, 0-15 wt% of Lian soil, 10-40 wt% of quartz and 20-45 wt% of feldspar.
The bottom coating comprises 10-30 wt% of alumina, 30-60 wt% of quartz, 10-25 wt% of limestone, 10-25 wt% of dolomite, 0-10 wt% of spodumene and 1-10 wt% of zinc oxide.
The surface coating is composed of polystyrene slurry with the concentration of 0.01-1 mol/L and a binder, wherein the binder is one or a combination of CMC, PVA and fluorinated polyurethane elastomer, and the polystyrene and the binder are in a molar ratio of 1: 0.1-0.4.
The intermediate transparent coating comprises the raw materials of 10-30 wt% of potash feldspar, 20-50 wt% of quartz, 7-19 wt% of limestone, 3-7 wt% of dolomite, 0-10 wt% of spodumene, 1-9 wt% of zinc oxide and 1-58 wt% of fusion cakes; wherein the frit has a chemical composition of SiO240~60wt%、K2O 1~10wt%、Na2O 1~10wt%、CaO 5~10wt%、Al2O36~17wt%、B2O35~17wt%。
The raw material compositions of the green body and the coating of the architectural ceramic tile of each example are shown in table 1; the chemical composition of the frit is shown in table 2.
TABLE 1 raw material composition of green body and coating of architectural ceramic tile of the invention
At a molar ratio of CMC + PVA of 1: 1
Table 2 chemical composition of frits of examples of the present invention
The embodiment discloses a preparation method of a super-hydrophobic building ceramic tile, which comprises the following steps:
(1) preparation of building ceramic tile green body
The raw materials of the building ceramic tile green body are proportioned and uniformly mixed according to the table 1, and are biscuit-fired at the temperature of 900 ℃ after ball milling, screening, ageing, stirring, refining, grouting and drying treatment, and the building ceramic tile green body is obtained after cooling;
(2) preparation of bottom coating slurry and intermediate transparent coating slurry
The raw materials of the bottom coating are proportioned and mixed uniformly as shown in table 1, and then are ball-milled and sieved to obtain uniform bottom coating slurry; preparing intermediate transparent coating slurry by the same method;
(3) preparation of bottom coat, intermediate clear coat
Uniformly coating the bottom coating slurry on the surface of the building ceramic tile green body, and drying in the shade to obtain the building ceramic tile green body with the bottom coating; or continuously coating the intermediate transparent coating slurry on the bottom coating, and drying in the shade to obtain a green body of the architectural ceramic tile with the intermediate transparent coating;
(4) preparation of polystyrene slurry
Mixing potassium hydroxide and a styrene monomer according to the volume ratio of 1: 1, carrying out ultrasonic treatment for 15min, standing for 60min, taking upper styrene, and adding a potassium persulfate solution with the concentration of 0.008mol/L and a hexadecyl trimethyl ammonium bromide solution with the concentration of 0.002 mol/L to form a mixed solution, wherein the volume ratio of the styrene monomer, the potassium persulfate solution and the hexadecyl trimethyl ammonium bromide solution is 1: 3; placing the mixed solution in a water bath at 80 ℃, heating and stirring for 2h, centrifugally cleaning for 5 times, and adding water to prepare polystyrene slurry with the concentration of 0.05 mol/L;
(5) preparation of surface coating slurries
Uniformly mixing the polystyrene slurry and the binder according to the molar ratio of 1: 0.2 to obtain surface coating slurry;
(6) preparation of surface coatings
Uniformly spraying the surface coating slurry on a building ceramic tile blank with a bottom coating or a building ceramic tile blank with a middle transparent coating by adopting a spraying method, wherein the spraying air pressure is 0.5MPa, the diameter of a nozzle is 3mm, and the distance between the nozzle and a substrate coating is 8 cm; and then placing the ceramic tile at the temperature of 180 ℃ for baking for 20min to obtain the super-hydrophobic building ceramic tile.
Example two preparation methods of a superhydrophobic architectural ceramic tile, comprising the steps of:
(1) preparation of building ceramic tile green body
The raw materials of the building ceramic tile green body are proportioned and uniformly mixed according to the table 1, and are biscuit-fired at the temperature of 900 ℃ after ball milling, screening, ageing, stirring, refining, grouting and drying treatment, and the building ceramic tile green body is obtained after cooling;
(2) preparation of bottom coating slurry and intermediate transparent coating slurry
The raw materials of the bottom coating are proportioned and mixed uniformly as shown in table 1, and then are ball-milled and sieved to obtain uniform bottom coating slurry; preparing intermediate transparent coating slurry by the same method;
(3) preparation of bottom coat, intermediate clear coat
Uniformly coating the bottom coating slurry on the surface of the building ceramic tile green body, and drying in the shade to obtain the building ceramic tile green body with the bottom coating; or continuously coating the intermediate transparent coating slurry on the bottom coating, and drying in the shade to obtain a green body of the architectural ceramic tile with the intermediate transparent coating;
(4) preparation of polystyrene slurry
Mixing potassium hydroxide and a styrene monomer according to the volume ratio of 1: 1, carrying out ultrasonic treatment for 20min, standing for 60min, taking upper styrene, and adding a potassium persulfate solution with the concentration of 0.003mol/L and a hexadecyl trimethyl ammonium bromide solution with the concentration of 0.005mol to form a mixed solution, wherein the volume ratio of the styrene monomer, the potassium persulfate solution and the hexadecyl trimethyl ammonium bromide solution is 1: 6; heating and stirring the mixed solution in a water bath at 70 ℃ for 8h, centrifugally cleaning for 15 times, and adding water to prepare polystyrene slurry with the concentration of 0.06 mol/L;
(5) preparation of surface coating slurries
Uniformly mixing the polystyrene slurry and the binder according to the molar ratio of 1: 0.2 to obtain surface coating slurry;
(6) preparation of surface coatings
Uniformly spraying the surface coating slurry on a building ceramic tile blank with a bottom coating or a building ceramic tile blank with a middle transparent coating by adopting a spraying method, wherein the spraying air pressure is 0.25MPa, the diameter of a nozzle is 2mm, and the distance between the nozzle and a substrate coating is 9 cm; and then placing the ceramic tile at the temperature of 120 ℃ for drying for 16min to obtain the super-hydrophobic building ceramic tile.
The preparation method of the super-hydrophobic building ceramic tile comprises the following steps:
(1) preparation of building ceramic tile green body
The raw materials of the ceramic tile green body are proportioned and uniformly mixed according to the table 1, and are biscuit fired at the temperature of 800 ℃ after ball milling, sieving, ageing, stirring, refining, grouting and drying treatment, and the building ceramic tile green body is obtained after cooling;
(2) preparation of bottom coating slurry and intermediate transparent coating slurry
The raw materials of the bottom coating are proportioned and mixed uniformly as shown in table 1, and then are ball-milled and sieved to obtain uniform bottom coating slurry; preparing intermediate transparent coating slurry by the same method;
(3) preparation of bottom coat, intermediate clear coat
Uniformly coating the bottom coating slurry on the surface of the building ceramic tile green body, and drying in the shade to obtain the building ceramic tile green body with the bottom coating; or continuously coating the intermediate transparent coating slurry on the bottom coating, and drying in the shade to obtain a green body of the architectural ceramic tile with the intermediate transparent coating;
(4) preparation of polystyrene slurry
Mixing potassium hydroxide and a styrene monomer according to the volume ratio of 1: 1, carrying out ultrasonic treatment for 20min, standing for 60min, taking upper styrene, and adding a potassium persulfate solution with the concentration of 0.001mol/L and a hexadecyl trimethyl ammonium bromide solution with the concentration of 0.001mol/L to form a mixed solution, wherein the volume ratio of the styrene monomer, the potassium persulfate solution and the hexadecyl trimethyl ammonium bromide solution is 1: 2; placing the mixed solution in a water bath at 60 ℃, heating and stirring for 8h, centrifugally cleaning for 2 times, and adding water to prepare polystyrene slurry with the concentration of 0.04 mol/L;
(5) preparation of surface coating slurries
Uniformly mixing the polystyrene slurry and the binder according to the molar ratio of 1: 0.3 to obtain surface coating slurry;
(6) preparation of surface coatings
Uniformly spraying the surface coating slurry on a building ceramic tile blank with a bottom coating or a building ceramic tile blank with a middle transparent coating by adopting a spraying method, wherein the spraying air pressure is 3MPa, the diameter of a nozzle is 2mm, and the distance between the nozzle and a substrate coating is 16 cm; and then placing the mixture into a temperature of 170 ℃ for baking for 34min to obtain the super-hydrophobic building ceramic tile.
The preparation method of the super-hydrophobic building ceramic tile comprises the following steps:
(1) preparation of building ceramic tile green body
The raw materials of the ceramic tile green body are proportioned and mixed uniformly according to the table 1, and the building ceramic tile green body is obtained after ball milling, sieving, ageing, stirring, refining, grouting and drying treatment, biscuit firing at 1100 ℃ and cooling;
(2) preparation of bottom coating slurry and intermediate transparent coating slurry
The raw materials of the bottom coating are proportioned and mixed uniformly as shown in table 1, and then are ball-milled and sieved to obtain uniform bottom coating slurry; preparing intermediate transparent coating slurry by the same method;
(3) preparation of bottom coat, intermediate clear coat
Uniformly coating the bottom coating slurry on the surface of the building ceramic tile green body, and drying in the shade to obtain the building ceramic tile green body with the bottom coating; or continuously coating the intermediate transparent coating slurry on the bottom coating, and drying in the shade to obtain a green body of the architectural ceramic tile with the intermediate transparent coating;
(4) preparation of polystyrene slurry
Mixing potassium hydroxide and a styrene monomer according to the volume ratio of 1: 1, carrying out ultrasonic treatment for 15min, standing for 60min, taking upper styrene, and adding a potassium persulfate solution with the concentration of 0.05mol/L and a hexadecyl trimethyl ammonium bromide solution with the concentration of 0.02mol to form a mixed solution, wherein the volume ratio of the styrene monomer, the potassium persulfate solution and the hexadecyl trimethyl ammonium bromide solution is 1: 5; placing the mixed solution in a water bath at 80 ℃, heating and stirring for 10 h, centrifugally cleaning for 5 times, and adding water to prepare polystyrene slurry with the concentration of 0.04 mol/L;
(5) preparation of surface coating slurries
Uniformly mixing the polystyrene slurry and the binder according to the molar ratio of 1: 0.4 to obtain surface coating slurry;
(6) preparation of surface coatings
Uniformly spraying the surface coating slurry on a building ceramic tile blank with a bottom coating or a building ceramic tile blank with a middle transparent coating by adopting a spraying method, wherein the spraying air pressure is 0.8MPa, the diameter of a nozzle is 2mm, and the distance between the nozzle and a substrate coating is 10 cm; and then placing the ceramic tile at the temperature of 180 ℃ for baking for 30min to obtain the super-hydrophobic building ceramic tile.
The performance indexes of the super-hydrophobic building ceramic tile prepared by the embodiment of the invention are shown in Table 3.
TABLE 3 Performance indices of superhydrophobic architectural ceramic tiles prepared according to embodiments of the invention

Claims (7)

1. A super-hydrophobic building ceramic tile is characterized in that: the building ceramic tile is composed of a building ceramic tile body and a composite coating coated on the surface of the building ceramic tile body; the composite coating is at least two layers, namely a bottom coating and a surface coating; the raw materials of the building ceramic tile blank body comprise 5-20 wt% of Jiepai soil, 5-25 wt% of Minqing soil, 0-15 wt% of Lian soil, 10-40 wt% of quartz and 20-45 wt% of feldspar; the bottom coating comprises the following raw materials of 10-30 wt% of alumina, 30-60 wt% of quartz, 10-25 wt% of limestone, 10-25 wt% of dolomite, 0-10 wt% of spodumene and 1-10 wt% of zinc oxide; the surface coating is composed of polystyrene slurry with the concentration of 0.01-1 mol/L and a binder, wherein the binder is one or a combination of CMC, PVA and fluorinated polyurethane elastomer, and the polystyrene slurry and the binder are in a molar ratio of 1: 0.1-0.4.
2. The superhydrophobic architectural ceramic tile of claim 1, wherein: the composite coating further comprises an intermediate clear coat layer positioned between the base coat layer and the top coat layer; the intermediate transparent coating comprises the following raw materials of 10-30 wt% of potash feldspar, 20-50 wt% of quartz, 7-19 wt% of limestone, 3-7 wt% of dolomite, 0-10 wt% of spodumene, 1-9 wt% of zinc oxide and 1-58 wt% of fusion cakes.
3. Superphobic as in claim 2The water building ceramic tile is characterized in that: the frit has a chemical composition of SiO240~60wt%、K2O 1~10wt%、Na2O 1~10wt%、CaO 5~10wt%、Al2O36~17wt%、B2O3 5~17wt%。
4. A method for the preparation of the superhydrophobic architectural ceramic tile according to one of claims-3, characterized in that it comprises the steps of:
(1) preparation of building ceramic tile green body
Mixing the raw materials of the building ceramic tile green body uniformly according to a ratio, performing ball milling, sieving, ageing, stirring, refining, grouting, drying and biscuit firing treatment, and cooling to obtain a building ceramic tile green body;
(2) preparation of bottom coating slurry and intermediate transparent coating slurry
Uniformly mixing the raw materials of the bottom coating according to a ratio, and performing ball milling and sieving to obtain uniform bottom coating slurry; preparing intermediate transparent coating slurry by the same method;
(3) preparation of bottom coat, intermediate clear coat
Uniformly coating the bottom coating slurry on the surface of a building ceramic tile green body, and drying in the shade to obtain the building ceramic tile green body with the bottom coating; or continuously coating the intermediate transparent coating slurry on the bottom coating, and drying in the shade to obtain a green body of the architectural ceramic tile with the intermediate transparent coating;
(4) preparation of polystyrene slurry
Mixing potassium hydroxide and a styrene monomer according to the volume ratio of 1: 1, carrying out ultrasonic treatment for 10-60 min, standing, taking upper styrene, and adding a potassium persulfate solution with the concentration of 0.001-0.05 mol/L and a hexadecyl trimethyl ammonium bromide solution with the concentration of 0.001-0.07 mol/L to form a mixed solution; wherein, the volume ratio of the styrene monomer to the potassium persulfate solution to the hexadecyl trimethyl ammonium bromide solution is 1: 0.1-6; placing the mixed solution in a water bath at the temperature of 60-100 ℃, and heating and stirring for 1-50 h; centrifugally cleaning for 2-30 times, and adding water to prepare polystyrene slurry with the concentration of 0.01-1 mol/L;
(5) preparation of surface coating slurries
Uniformly mixing the polystyrene slurry and a binder according to a ratio to obtain surface coating slurry;
(6) preparation of surface coatings
And uniformly spraying the surface coating slurry on a building ceramic tile blank body with a bottom coating or a building ceramic tile blank body with a middle transparent coating by adopting a spraying method, and drying to obtain the super-hydrophobic building ceramic tile.
5. The method for preparing a superhydrophobic architectural ceramic tile according to claim 4, wherein: the bisque firing temperature in the step (1) is 600-1300 ℃.
6. The method for preparing a superhydrophobic architectural ceramic tile according to claim 4, wherein: the spraying method in the step (6) is as follows: the air pressure of spraying is 0.1-5 MPa, the diameter of a nozzle is 1-5 mm, and the distance between the nozzle and a substrate coating is 1-20 cm.
7. The method for preparing a superhydrophobic architectural ceramic tile according to claim 4, wherein: and (3) drying at the temperature of 80-280 ℃ for 1-60 min in the step (6).
CN202111065188.4A 2021-09-11 2021-09-11 Super-hydrophobic building ceramic tile and preparation method thereof Pending CN114105684A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
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Application Number Priority Date Filing Date Title
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Publications (1)

Publication Number Publication Date
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