CN112250308A - Natural-imitated granite ceramic tile with antifouling effect and preparation method thereof - Google Patents
Natural-imitated granite ceramic tile with antifouling effect and preparation method thereof Download PDFInfo
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- CN112250308A CN112250308A CN202011292728.8A CN202011292728A CN112250308A CN 112250308 A CN112250308 A CN 112250308A CN 202011292728 A CN202011292728 A CN 202011292728A CN 112250308 A CN112250308 A CN 112250308A
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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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
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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
- C03C4/00—Compositions for glass with special properties
- C03C4/02—Compositions for glass with special properties for coloured glass
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- 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
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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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/20—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing titanium compounds; containing zirconium compounds
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
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- C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/86—Glazes; Cold glazes
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Abstract
The invention discloses an artificial natural granite ceramic tile with antifouling function and a preparation method thereof, wherein the tile comprises a tile blank and a glaze layer from bottom to top; the glaze layer is formed by mixing three or more than three kinds of suspension slurry of white particle suspension slurry, black particle suspension slurry, red particle suspension slurry and brown particle suspension slurry and spraying the mixture on a ceramic tile blank body for firing. The ceramic tile is prepared by mixing three or more than three kinds of suspension slurry of white particle suspension slurry, black particle suspension slurry, red particle suspension slurry and brown particle suspension slurry and spraying the mixture on a ceramic tile blank to fire; through the granule suspension thick liquid that uses different colours to the size of control granule sprays it on the ceramic tile body, can reach natural lifelike natural granite effect, modified titanium dioxide through doping biological charcoal in the titanium dioxide crystal lattice, be favorable to adjusting the motion condition in photoproduction electron and hole, reduce the energy band, also can increase specific surface area simultaneously, thereby show improvement antifouling effect.
Description
Technical Field
The invention relates to the technical field of building materials, in particular to an artificial natural granite ceramic tile with an antifouling effect and a preparation method thereof.
Background
At present, in the production process of ceramic wall and floor tiles, ceramic tiles imitating natural stone textures gradually become mainstream and are increasingly popular with consumers. There are two common methods for displaying the texture of natural stone, which are screen printing and grid stripe cloth, respectively. The silk-screen printing method has larger defects, and the formed texture lines have the defects of overlarge lines, dead plates and poor simulation compared with the texture lines of natural stone. Meanwhile, the silk-screen printing has the defects of extremely limited colors and insufficient brightness of color development. The grid stripe distribution method can only manufacture some rough and rough texture lines, the texture is limited by the distribution grid, and the texture can only present the same approximate pattern as the grid monotonously, and cannot present the sense of fineness and the layering effect of the texture lines of the natural stone.
At present, antifouling ceramic is prepared by vacuum evaporation of antifouling film material on the surface of ceramic, so that the surface of ceramic is not easy to be polluted, but the antifouling film is easy to fall off after long-time use. This is because the ceramic surface and the antifouling film are connected by van der waals force, which is extremely weak and easily broken, resulting in detachment of the antifouling film.
Disclosure of Invention
The invention provides an imitated natural granite ceramic tile with an antifouling effect and a preparation method thereof.
The invention adopts the following technical scheme for solving the technical problems:
an antifouling imitated natural granite ceramic tile comprises a ceramic tile blank and a glaze layer from bottom to top; the glaze layer is formed by mixing three or more than three kinds of suspension slurry of white particle suspension slurry, black particle suspension slurry, red particle suspension slurry and brown particle suspension slurry and spraying the mixture on a ceramic tile blank body for firing.
As a preferable scheme, the white particle suspension slurry is prepared from the following raw materials in parts by weight: 10-20 parts of mullite, 5-15 parts of kaolin, 5-10 parts of talc, 15-30 parts of albite, 5-15 parts of quartz powder, 6-10 parts of barium oxide, 4-8 parts of alumina, 3-8 parts of an antifouling material, 4-8 parts of titanium dioxide, 0.8-2 parts of sodium carboxymethylcellulose and 1-4 parts of zirconia.
As a preferable scheme, the black particle suspension pulp is prepared from the following raw materials in parts by weight: 10-20 parts of mullite, 5-15 parts of kaolin, 5-10 parts of talc, 15-30 parts of albite, 5-15 parts of quartz powder, 6-10 parts of barium oxide, 4-8 parts of alumina, 3-8 parts of an antifouling material, 4-8 parts of modified titanium dioxide, 0.8-2 parts of sodium carboxymethylcellulose, 1-4 parts of zirconia and 2-5 parts of a black pigment; the black pigment is cobalt oxide.
As a preferable scheme, the preparation method of the modified titanium dioxide comprises the following steps: adding 1-3 parts of titanium dioxide into 10-15 parts of acetone, adding 0.5-1.5 parts of biochar and 0.1-0.4 part of KH570, carrying out ultrasonic treatment for 20-40 min at 400-600W, filtering, carrying out vacuum drying, calcining for 60-100 min at 300-400 ℃, and grinding to 100-200 meshes to obtain the modified titanium dioxide.
The titanium dioxide absorbs short-wave light radiation with energy higher than the forbidden band width of the titanium dioxide, generates electron transition and corresponding holes, transfers the energy to surrounding media, induces chemical reaction, has photocatalysis capacity, and can decompose organic matters by the reaction products of electrons and holes generated by photocatalysis, water and oxygen, thereby having antifouling effect.
As a preferable scheme, the red particle suspension pulp is prepared from the following raw materials in parts by weight: 10-20 parts of mullite, 5-15 parts of kaolin, 5-10 parts of talc, 15-30 parts of albite, 5-15 parts of quartz powder, 6-10 parts of barium oxide, 4-8 parts of alumina, 3-8 parts of an antifouling material, 4-8 parts of titanium dioxide, 0.8-2 parts of sodium carboxymethylcellulose, 1-4 parts of zirconia and 2-5 parts of a red pigment; the red pigment is iron oxide red.
As a preferable scheme, the brown particle suspension slurry is prepared from the following raw materials in parts by weight: 10-20 parts of mullite, 5-15 parts of kaolin, 5-10 parts of talc, 15-30 parts of albite, 5-15 parts of quartz powder, 6-10 parts of barium oxide, 4-8 parts of alumina, 3-8 parts of an antifouling material, 4-8 parts of titanium dioxide, 0.8-2 parts of sodium carboxymethylcellulose, 1-4 parts of zirconia and 2-5 parts of brown pigment; the brown pigment is iron chromium brown.
As a preferable scheme, the preparation method of the antifouling material comprises the following steps: adding 0.5-2 parts of calcium carbonate, 0.5-2 parts of tin oxide and 0.8-2 parts of aluminum oxide into a mixer, uniformly mixing to obtain a mixture, adding the mixture into 0.5-3 wt% of phosphoric acid aqueous solution, stirring at the rotating speed of 60-150 rpm for 4-8 hours to obtain slurry, adding 1-4 parts of lanthanum nitrate into the slurry, stirring at the rotating speed of 60-150 rpm for 2-5 hours, filtering, drying, keeping the temperature in a muffle furnace at 450-600 ℃ for 2-5 hours, and grinding to 100-200 meshes to obtain the antifouling material.
The antifouling material is a rare earth composite phosphate formed by calcium carbonate, tin oxide, aluminum oxide, lanthanum nitrate and phosphoric acid, and can activate water molecules, reduce the surface tension of water, increase a contact angle and improve the stability of a formula after contacting with water, so that the antifouling material has a good antifouling effect.
The invention also provides a preparation method of the natural granite-imitated ceramic tile with the antifouling effect, which comprises the following steps:
s1: preparing white particle suspension slurry, black particle suspension slurry, red particle suspension slurry and brown particle suspension slurry;
s2: mixing three or more than three kinds of suspension pulp of white particle suspension pulp, black particle suspension pulp, red particle suspension pulp and brown particle suspension pulp to obtain mixed pulp;
s3: spraying the mixed slurry on the surface of a ceramic tile blank with a smooth surface, and drying at 250-280 ℃ in a drying kiln;
s4: after drying, conveying the mixture to a roller kiln for sintering;
s5: and (3) edging the semi-finished brick by using conventional edging processing equipment to obtain the antifouling imitated natural granite ceramic tile.
As a preferable scheme, the spraying amount in the S3 is 500-700 ml/m2。
Preferably, in the step S4, the firing temperature is 1150-1300 ℃, and the firing time is 60-90 min.
The invention has the beneficial effects that: (1) the ceramic tile is prepared by mixing three or more than three kinds of suspension slurry of white particle suspension slurry, black particle suspension slurry, red particle suspension slurry and brown particle suspension slurry and spraying the mixture on a ceramic tile blank to fire; the modified titanium dioxide is sprayed on a tile blank by using the particle suspension slurries with different colors, controlling the sizes of the particles and controlling the proportion of the suspension slurries with different colors, so that the natural and vivid natural granite effect can be achieved, the texture is fine, the use of the natural granite can be effectively avoided, and the resources are effectively saved, (2) the modified titanium dioxide is beneficial to adjusting the motion conditions of photoproduction electrons and cavities by doping biochar in titanium dioxide crystal lattices, the energy band is reduced, and meanwhile, the specific surface area can be increased, so that the antifouling effect is obviously improved; (3) the antifouling material disclosed by the invention is a rare earth composite phosphate formed by calcium carbonate, tin oxide, aluminum oxide, lanthanum nitrate and phosphoric acid, and can activate water molecules, reduce the surface tension of water, increase a contact angle and improve the stability of a formula after contacting with water, so that the antifouling material has a good antifouling effect.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless otherwise stated, the parts are weight parts.
Example 1
The natural granite-like ceramic tile with antifouling effect comprises a ceramic tile blank and a glaze layer from bottom to top, wherein the glaze layer is formed by mixing white particle suspension slurry, black particle suspension slurry and red particle suspension slurry and spraying the mixture on the ceramic tile blank to be fired.
The white particle suspension slurry is prepared from the following raw materials in parts by weight: 18 parts of mullite, 10 parts of kaolin, 6 parts of talc, 22 parts of albite, 8 parts of quartz powder, 7 parts of barium oxide, 5 parts of alumina, 5 parts of an antifouling material, 5 parts of titanium dioxide, 1.2 parts of sodium carboxymethylcellulose and 2.8 parts of zirconia.
The black particle suspension slurry is prepared from the following raw materials in parts by weight: 18 parts of mullite, 10 parts of kaolin, 6 parts of talc, 22 parts of albite, 8 parts of quartz powder, 7 parts of barium oxide, 5 parts of alumina, 5 parts of an antifouling material, 5 parts of modified titanium dioxide, 1.2 parts of sodium carboxymethylcellulose, 2.8 parts of zirconia and 4 parts of a black pigment; the black pigment is cobalt oxide.
The preparation method of the modified titanium dioxide comprises the following steps: adding 1.8 parts of titanium dioxide into 12 parts of acetone, adding 0.8 part of biochar and 0.25 part of KH570, carrying out ultrasonic treatment for 30min at 500W, filtering, drying in vacuum, calcining for 80min at 380 ℃, and grinding to 150 meshes to obtain the modified titanium dioxide.
The red particle suspension slurry is prepared from the following raw materials in parts by weight: 18 parts of mullite, 10 parts of kaolin, 6 parts of talc, 22 parts of albite, 8 parts of quartz powder, 7 parts of barium oxide, 5 parts of alumina, 5 parts of an antifouling material, 5 parts of titanium dioxide, 1.2 parts of sodium carboxymethylcellulose, 2.8 parts of zirconia and 4 parts of a red pigment; the red pigment is iron oxide red.
The preparation method of the antifouling material comprises the following steps: adding 0.8 part of calcium carbonate, 1 part of tin oxide and 1.5 parts of aluminum oxide into a mixer, uniformly mixing to obtain a mixture, adding the mixture into 2wt% phosphoric acid aqueous solution, stirring at the rotating speed of 100rpm for 6 hours to obtain slurry, adding 2.5 parts of lanthanum nitrate into the slurry, stirring at the rotating speed of 100rpm for 3 hours, filtering, drying, preserving the temperature in a muffle furnace at 500 ℃ for 4 hours, and grinding to 150 meshes to obtain the antifouling material.
The preparation method of the imitated natural granite ceramic tile with the antifouling effect comprises the following steps:
s1: preparing white particle suspension pulp, black particle suspension pulp and red particle suspension pulp;
s11: mixing mullite, kaolin, talc, albite, quartz powder, barium oxide and alumina in proportion, melting at 1400 ℃ for 7 hours to obtain a frit, crushing to 80 meshes, adding the frit, an antifouling material, titanium dioxide, sodium carboxymethylcellulose and zirconium oxide into a ball mill, and ball-milling to obtain white particle suspension slurry;
s12: mixing mullite, kaolin, talc, albite, quartz powder, barium oxide and alumina in proportion, melting for 7 hours at 1400 ℃ to obtain a frit, crushing to 150 meshes, adding the frit, an antifouling material, modified titanium dioxide, sodium carboxymethylcellulose, zirconium oxide and cobalt oxide into a ball mill, and ball-milling to obtain black particle suspension slurry;
s13: mixing mullite, kaolin, talc, albite, quartz powder, barium oxide and alumina in proportion, melting at 1400 ℃ for 7 hours to obtain a frit, crushing to 100 meshes, adding the frit, an antifouling material, titanium dioxide, sodium carboxymethylcellulose, zirconium oxide and iron oxide red into a ball mill, and ball-milling to obtain red particle suspension slurry;
s2: white particle suspension pulp, black particle suspension pulp and red particle suspension pulp are mixed according to the weight ratio of 4: 3: 3 mixing to obtain mixed slurry;
s3: spraying the mixed slurry on the surface of a ceramic tile green body with a smooth surface, and drying at 260 ℃ in a drying kiln, wherein the spraying amount is 600 ml/m2；
S4: drying, conveying to a roller kiln, and sintering at 1200 ℃ for 80 min;
s5: and (3) edging the semi-finished brick by using conventional edging processing equipment to obtain the antifouling imitated natural granite ceramic tile.
Example 2
The natural granite-like ceramic tile with antifouling effect comprises a ceramic tile blank and a glaze layer from bottom to top, wherein the glaze layer is formed by mixing white particle suspension slurry, black particle suspension slurry and brown particle suspension slurry and spraying the mixture on the ceramic tile blank to fire.
The white particle suspension slurry is prepared from the following raw materials in parts by weight: 18 parts of mullite, 10 parts of kaolin, 6 parts of talc, 22 parts of albite, 8 parts of quartz powder, 7 parts of barium oxide, 5 parts of alumina, 5 parts of an antifouling material, 5 parts of titanium dioxide, 1.2 parts of sodium carboxymethylcellulose and 2.8 parts of zirconia.
The black particle suspension slurry is prepared from the following raw materials in parts by weight: 18 parts of mullite, 10 parts of kaolin, 6 parts of talc, 22 parts of albite, 8 parts of quartz powder, 7 parts of barium oxide, 5 parts of alumina, 5 parts of an antifouling material, 5 parts of modified titanium dioxide, 1.2 parts of sodium carboxymethylcellulose, 2.8 parts of zirconia and 4 parts of a black pigment; the black pigment is cobalt oxide.
The preparation method of the modified titanium dioxide comprises the following steps: adding 1.8 parts of titanium dioxide into 12 parts of acetone, adding 0.8 part of biochar and 0.25 part of KH570, carrying out ultrasonic treatment for 30min at 500W, filtering, drying in vacuum, calcining for 80min at 380 ℃, and grinding to 150 meshes to obtain the modified titanium dioxide.
The brown particle suspension slurry is prepared from the following raw materials in parts by weight: 18 parts of mullite, 10 parts of kaolin, 6 parts of talc, 22 parts of albite, 8 parts of quartz powder, 7 parts of barium oxide, 5 parts of alumina, 5 parts of an antifouling material, 5 parts of titanium dioxide, 1.2 parts of sodium carboxymethylcellulose, 2.8 parts of zirconia and 4 parts of brown pigment; the brown pigment is iron chromium brown.
The preparation method of the antifouling material comprises the following steps: adding 0.8 part of calcium carbonate, 1 part of tin oxide and 1.5 parts of aluminum oxide into a mixer, uniformly mixing to obtain a mixture, adding the mixture into 2wt% phosphoric acid aqueous solution, stirring at the rotating speed of 100rpm for 6 hours to obtain slurry, adding 2.5 parts of lanthanum nitrate into the slurry, stirring at the rotating speed of 100rpm for 3 hours, filtering, drying, preserving the temperature in a muffle furnace at 500 ℃ for 4 hours, and grinding to 150 meshes to obtain the antifouling material.
The preparation method of the imitated natural granite ceramic tile with the antifouling effect comprises the following steps:
s1: preparing white particle suspension slurry, black particle suspension slurry and brown particle suspension slurry;
s11: mixing mullite, kaolin, talc, albite, quartz powder, barium oxide and alumina in proportion, melting at 1400 ℃ for 7 hours to obtain a frit, crushing to 80 meshes, adding the frit, an antifouling material, titanium dioxide, sodium carboxymethylcellulose and zirconium oxide into a ball mill, and ball-milling to obtain white particle suspension slurry;
s12: mixing mullite, kaolin, talc, albite, quartz powder, barium oxide and alumina in proportion, melting for 7 hours at 1400 ℃ to obtain a frit, crushing to 150 meshes, adding the frit, an antifouling material, modified titanium dioxide, sodium carboxymethylcellulose, zirconium oxide and cobalt oxide into a ball mill, and ball-milling to obtain black particle suspension slurry;
s13: mixing mullite, kaolin, talc, albite, quartz powder, barium oxide and alumina in proportion, melting at 1400 ℃ for 7 hours to obtain a frit, crushing to 100 meshes, adding the frit, an antifouling material, titanium dioxide, sodium carboxymethylcellulose and iron chromium brown into a ball mill, and carrying out ball milling to obtain brown particle suspension slurry;
s2: white particle suspension slurry, black particle suspension slurry and brown particle suspension slurry are mixed according to the weight ratio of 4: 3: 3 mixing to obtain mixed slurry;
s3: spraying the mixed slurry on the surface of a ceramic tile green body with a smooth surface, and drying at 260 ℃ in a drying kiln, wherein the spraying amount is 600 ml/m2；
S4: drying, conveying to a roller kiln, and sintering at 1200 ℃ for 80 min;
s5: and (3) edging the semi-finished brick by using conventional edging processing equipment to obtain the antifouling imitated natural granite ceramic tile.
Example 3
The natural granite-like ceramic tile with antifouling effect comprises a ceramic tile blank and a glaze layer from bottom to top, wherein the glaze layer is formed by mixing black particle suspension slurry, red particle suspension slurry and brown particle suspension slurry and spraying the mixture on the ceramic tile blank to fire.
The black particle suspension slurry is prepared from the following raw materials in parts by weight: 18 parts of mullite, 10 parts of kaolin, 6 parts of talc, 22 parts of albite, 8 parts of quartz powder, 7 parts of barium oxide, 5 parts of alumina, 5 parts of an antifouling material, 5 parts of modified titanium dioxide, 1.2 parts of sodium carboxymethylcellulose, 2.8 parts of zirconia and 4 parts of a black pigment; the black pigment is cobalt oxide.
The preparation method of the modified titanium dioxide comprises the following steps: adding 1.8 parts of titanium dioxide into 12 parts of acetone, adding 0.8 part of biochar and 0.25 part of KH570, carrying out ultrasonic treatment for 30min at 500W, filtering, drying in vacuum, calcining for 80min at 380 ℃, and grinding to 150 meshes to obtain the modified titanium dioxide.
The red particle suspension slurry is prepared from the following raw materials in parts by weight: 18 parts of mullite, 10 parts of kaolin, 6 parts of talc, 22 parts of albite, 8 parts of quartz powder, 7 parts of barium oxide, 5 parts of alumina, 5 parts of an antifouling material, 5 parts of titanium dioxide, 1.2 parts of sodium carboxymethylcellulose, 2.8 parts of zirconia and 4 parts of a red pigment; the red pigment is iron oxide red.
The brown particle suspension slurry is prepared from the following raw materials in parts by weight: 18 parts of mullite, 10 parts of kaolin, 6 parts of talc, 22 parts of albite, 8 parts of quartz powder, 7 parts of barium oxide, 5 parts of alumina, 5 parts of an antifouling material, 5 parts of titanium dioxide, 1.2 parts of sodium carboxymethylcellulose, 2.8 parts of zirconia and 4 parts of brown pigment; the brown pigment is iron chromium brown.
The preparation method of the antifouling material comprises the following steps: adding 0.8 part of calcium carbonate, 1 part of tin oxide and 1.5 parts of aluminum oxide into a mixer, uniformly mixing to obtain a mixture, adding the mixture into 2wt% phosphoric acid aqueous solution, stirring at the rotating speed of 100rpm for 6 hours to obtain slurry, adding 2.5 parts of lanthanum nitrate into the slurry, stirring at the rotating speed of 100rpm for 3 hours, filtering, drying, preserving the temperature in a muffle furnace at 500 ℃ for 4 hours, and grinding to 150 meshes to obtain the antifouling material.
The preparation method of the imitated natural granite ceramic tile with the antifouling effect comprises the following steps:
s1: preparing black particle suspension pulp, red particle suspension pulp and brown particle suspension pulp;
s11: mixing mullite, kaolin, talc, albite, quartz powder, barium oxide and alumina in proportion, melting for 7 hours at 1400 ℃ to obtain a frit, crushing to 150 meshes, adding the frit, an antifouling material, modified titanium dioxide, sodium carboxymethylcellulose, zirconium oxide and cobalt oxide into a ball mill, and ball-milling to obtain black particle suspension slurry;
s12: mixing mullite, kaolin, talc, albite, quartz powder, barium oxide and alumina in proportion, melting at 1400 ℃ for 7 hours to obtain a frit, crushing to 100 meshes, adding the frit, an antifouling material, titanium dioxide, sodium carboxymethylcellulose, zirconium oxide and iron oxide red into a ball mill, and ball-milling to obtain red particle suspension slurry;
s13: mixing mullite, kaolin, talc, albite, quartz powder, barium oxide and alumina in proportion, melting at 1400 ℃ for 7 hours to obtain a frit, crushing to 100 meshes, adding the frit, an antifouling material, titanium dioxide, sodium carboxymethylcellulose and iron chromium brown into a ball mill, and carrying out ball milling to obtain brown particle suspension slurry;
s2: mixing black particle suspension pulp, red particle suspension pulp and brown particle suspension pulp according to the weight ratio of 3: 4: 3 mixing to obtain mixed slurry;
s3: spraying the mixed slurry on the surface of a ceramic tile green body with a smooth surface, and drying at 260 ℃ in a drying kiln, wherein the spraying amount is 600 ml/m2；
S4: drying, conveying to a roller kiln, and sintering at 1200 ℃ for 80 min;
s5: and (3) edging the semi-finished brick by using conventional edging processing equipment to obtain the antifouling imitated natural granite ceramic tile.
Example 4
The natural granite-like ceramic tile with antifouling effect comprises a ceramic tile blank and a glaze layer from bottom to top, wherein the glaze layer is formed by mixing white particle suspension slurry, red particle suspension slurry and brown particle suspension slurry and spraying the mixture on the ceramic tile blank to fire.
The white particle suspension slurry is prepared from the following raw materials in parts by weight: 18 parts of mullite, 10 parts of kaolin, 6 parts of talc, 22 parts of albite, 8 parts of quartz powder, 7 parts of barium oxide, 5 parts of alumina, 5 parts of an antifouling material, 5 parts of titanium dioxide, 1.2 parts of sodium carboxymethylcellulose and 2.8 parts of zirconia.
The red particle suspension slurry is prepared from the following raw materials in parts by weight: 18 parts of mullite, 10 parts of kaolin, 6 parts of talc, 22 parts of albite, 8 parts of quartz powder, 7 parts of barium oxide, 5 parts of alumina, 5 parts of an antifouling material, 5 parts of titanium dioxide, 1.2 parts of sodium carboxymethylcellulose, 2.8 parts of zirconia and 4 parts of a red pigment; the red pigment is iron oxide red.
The brown particle suspension slurry is prepared from the following raw materials in parts by weight: 18 parts of mullite, 10 parts of kaolin, 6 parts of talc, 22 parts of albite, 8 parts of quartz powder, 7 parts of barium oxide, 5 parts of alumina, 5 parts of an antifouling material, 5 parts of titanium dioxide, 1.2 parts of sodium carboxymethylcellulose, 2.8 parts of zirconia and 4 parts of brown pigment; the brown pigment is iron chromium brown.
The preparation method of the antifouling material comprises the following steps: adding 0.8 part of calcium carbonate, 1 part of tin oxide and 1.5 parts of aluminum oxide into a mixer, uniformly mixing to obtain a mixture, adding the mixture into 2wt% phosphoric acid aqueous solution, stirring at the rotating speed of 100rpm for 6 hours to obtain slurry, adding 2.5 parts of lanthanum nitrate into the slurry, stirring at the rotating speed of 100rpm for 3 hours, filtering, drying, preserving the temperature in a muffle furnace at 500 ℃ for 4 hours, and grinding to 150 meshes to obtain the antifouling material.
The preparation method of the imitated natural granite ceramic tile with the antifouling effect comprises the following steps:
s1: preparing white particle suspension slurry, red particle suspension slurry and brown particle suspension slurry;
s11: mixing mullite, kaolin, talc, albite, quartz powder, barium oxide and alumina in proportion, melting at 1400 ℃ for 7 hours to obtain a frit, crushing to 80 meshes, adding the frit, an antifouling material, titanium dioxide, sodium carboxymethylcellulose and zirconium oxide into a ball mill, and ball-milling to obtain white particle suspension slurry;
s12: mixing mullite, kaolin, talc, albite, quartz powder, barium oxide and alumina in proportion, melting at 1400 ℃ for 7 hours to obtain a frit, crushing to 100 meshes, adding the frit, an antifouling material, titanium dioxide, sodium carboxymethylcellulose, zirconium oxide and iron oxide red into a ball mill, and ball-milling to obtain red particle suspension slurry;
s13: mixing mullite, kaolin, talc, albite, quartz powder, barium oxide and alumina in proportion, melting at 1400 ℃ for 7 hours to obtain a frit, crushing to 100 meshes, adding the frit, an antifouling material, titanium dioxide, sodium carboxymethylcellulose and iron chromium brown into a ball mill, and carrying out ball milling to obtain brown particle suspension slurry;
s2: white particle suspension slurry, red particle suspension slurry and brown particle suspension slurry are mixed according to the weight ratio of 4: 3: 3 mixing to obtain mixed slurry;
s3: spraying the mixed slurry on the surface of a ceramic tile green body with a smooth surface, and drying at 260 ℃ in a drying kiln, wherein the spraying amount is 600 ml/m2；
S4: drying, conveying to a roller kiln, and sintering at 1200 ℃ for 80 min;
s5: and (3) edging the semi-finished brick by using conventional edging processing equipment to obtain the antifouling imitated natural granite ceramic tile.
Example 5
Example 5 differs from example 1 in that the proportions of white particle suspension, black particle suspension and red particle suspension described in example 5 are different from example 1 in that the proportions of white particle suspension, black particle suspension and red particle suspension are again in the weight ratio of 4: 3: 3 mixing to obtain mixed slurry, and the rest is the same.
The white particle suspension slurry is prepared from the following raw materials in parts by weight: 10 parts of mullite, 5 parts of kaolin, 5 parts of talc, 15 parts of albite, 5 parts of quartz powder, 6 parts of barium oxide, 4 parts of alumina, 3 parts of an antifouling material, 4 parts of titanium dioxide, 0.8 part of sodium carboxymethylcellulose and 1 part of zirconia.
The black particle suspension slurry is prepared from the following raw materials in parts by weight: 10 parts of mullite, 5 parts of kaolin, 5 parts of talc, 15 parts of albite, 5 parts of quartz powder, 6 parts of barium oxide, 4 parts of alumina, 3 parts of an antifouling material, 4 parts of modified titanium dioxide, 0.8 part of sodium carboxymethylcellulose, 1 part of zirconia and 2 parts of a black pigment; the black pigment is cobalt oxide.
The red particle suspension slurry is prepared from the following raw materials in parts by weight: 10 parts of mullite, 5 parts of kaolin, 5 parts of talc, 15 parts of albite, 5 parts of quartz powder, 6 parts of barium oxide, 4 parts of alumina, 3 parts of an antifouling material, 4 parts of titanium dioxide, 0.8 part of sodium carboxymethylcellulose, 1 part of zirconia and 2 parts of a red pigment; the red pigment is iron oxide red.
Example 6
Example 6 differs from example 1 in that the proportions of white particle suspension, black particle suspension and red particle suspension described in example 6 are different from example 1 in that the proportions of white particle suspension, black particle suspension and red particle suspension are again in the weight ratio of 4: 3: 3 mixing to obtain mixed slurry, and the rest is the same.
The white particle suspension slurry is prepared from the following raw materials in parts by weight: 20 parts of mullite, 15 parts of kaolin, 10 parts of talc, 30 parts of albite, 15 parts of quartz powder, 10 parts of barium oxide, 8 parts of alumina, 8 parts of an antifouling material, 8 parts of titanium dioxide, 2 parts of sodium carboxymethylcellulose and 4 parts of zirconia.
The black particle suspension slurry is prepared from the following raw materials in parts by weight: 20 parts of mullite, 15 parts of kaolin, 10 parts of talc, 30 parts of albite, 15 parts of quartz powder, 10 parts of barium oxide, 8 parts of alumina, 8 parts of an antifouling material, 8 parts of modified titanium dioxide, 2 parts of sodium carboxymethylcellulose, 4 parts of zirconia and 5 parts of a black pigment; the black pigment is cobalt oxide.
The red particle suspension slurry is prepared from the following raw materials in parts by weight: 20 parts of mullite, 15 parts of kaolin, 10 parts of talc, 30 parts of albite, 15 parts of quartz powder, 10 parts of barium oxide, 8 parts of alumina, 8 parts of an antifouling material, 8 parts of titanium dioxide, 2 parts of sodium carboxymethylcellulose, 4 parts of zirconia and 5 parts of a red pigment; the red pigment is iron oxide red.
Comparative example 1
Comparative example 1 differs from example 1 in that the black particle suspension syrup described in comparative example 1 does not contain modified titanium dioxide, and the rest is the same.
Comparative example 2
Comparative example 2 is different from example 1 in that the black particle suspension slurry described in comparative example 2 is prepared by replacing the modified titanium dioxide with titanium dioxide, and the others are the same.
Comparative example 3
Comparative example 3 differs from example 1 in that the black particle suspension, white particle suspension, and red particle suspension described in comparative example 3 do not contain an antifouling material, and the others are the same.
Comparative example 4
Comparative example 4 is different from example 1 in that the antifouling material was prepared by a different method, and the others were the same.
The preparation method of the antifouling material comprises the following steps: adding 0.8 part of calcium carbonate, 1 part of tin oxide and 1.5 parts of aluminum oxide into a mixer, uniformly mixing to obtain a mixture, adding the mixture into 2wt% phosphoric acid aqueous solution, stirring at the rotating speed of 100rpm for 6 hours to obtain slurry, adding 2.5 parts of cerium nitrate into the slurry, stirring at the rotating speed of 100rpm for 3 hours, filtering, drying, keeping the temperature in a muffle furnace at 500 ℃ for 4 hours, and grinding to 150 meshes to obtain the antifouling material.
To further demonstrate the effect of the present invention, the following test methods were provided:
1. the antifouling property is detected according to GB/T3810.14-2006, the tile and water contact angle is tested by a JD-901C super-hydrophobic ceramic film water contact angle measuring instrument, and the test result is shown in Table 1.
TABLE 1 test results
As can be seen from Table 1, the natural stone-like tile with antifouling effect of the present invention has excellent antifouling property.
Comparative examples 1-4 show that different particle suspensions can affect the antifouling effect, wherein the combination of black particle suspension, white particle suspension and red particle suspension has the best antifouling effect.
It can be seen from comparative examples 1, 5 and 6 that different ratios of the black particle suspension, the white particle suspension and the red particle suspension can affect the antifouling effect, wherein example 1 is the best ratio.
It can be seen from comparison of example 1 with comparative examples 1 and 2 that the modified titanium dioxide in the black particle suspension slurry according to the present invention can affect the antifouling effect.
It is understood from the comparison of example 1 with comparative examples 3 and 4 that the antifouling material produced by the present invention can significantly improve the antifouling effect.
In light of the foregoing description of preferred embodiments according to the invention, it is clear that many changes and modifications can be made by the person skilled in the art without departing from the scope of the invention. The technical scope of the present invention is not limited to the contents of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. An antifouling imitated natural granite ceramic tile comprises a ceramic tile blank and a glaze layer from bottom to top; the ceramic tile is characterized in that the glaze layer is formed by mixing three or more than three kinds of suspension slurry of white particle suspension slurry, black particle suspension slurry, red particle suspension slurry and brown particle suspension slurry and spraying the mixture on a ceramic tile blank body for firing.
2. The natural-like granite tile with antifouling effect as claimed in claim 1, wherein the white particle suspension pulp is made of the following raw materials in parts by weight: 10-20 parts of mullite, 5-15 parts of kaolin, 5-10 parts of talc, 15-30 parts of albite, 5-15 parts of quartz powder, 6-10 parts of barium oxide, 4-8 parts of alumina, 3-8 parts of an antifouling material, 4-8 parts of titanium dioxide, 0.8-2 parts of sodium carboxymethylcellulose and 1-4 parts of zirconia.
3. The natural-like granite tile with antifouling effect as claimed in claim 1, wherein the black particle suspension pulp is made of the following raw materials in parts by weight: 10-20 parts of mullite, 5-15 parts of kaolin, 5-10 parts of talc, 15-30 parts of albite, 5-15 parts of quartz powder, 6-10 parts of barium oxide, 4-8 parts of alumina, 3-8 parts of an antifouling material, 4-8 parts of modified titanium dioxide, 0.8-2 parts of sodium carboxymethylcellulose, 1-4 parts of zirconia and 2-5 parts of a black pigment;
the black pigment is cobalt oxide.
4. The natural granite-like tile with antifouling effect as claimed in claim 3, wherein the modified titanium dioxide is prepared by the following steps: adding 1-3 parts of titanium dioxide into 10-15 parts of acetone, adding 0.5-1.5 parts of biochar and 0.1-0.4 part of KH570, carrying out ultrasonic treatment for 20-40 min at 400-600W, filtering, carrying out vacuum drying, calcining for 60-100 min at 300-400 ℃, and grinding to 100-200 meshes to obtain the modified titanium dioxide.
5. The natural-like granite tile with antifouling effect as claimed in claim 1, wherein the red particle suspension pulp is made of the following raw materials in parts by weight: 10-20 parts of mullite, 5-15 parts of kaolin, 5-10 parts of talc, 15-30 parts of albite, 5-15 parts of quartz powder, 6-10 parts of barium oxide, 4-8 parts of alumina, 3-8 parts of an antifouling material, 4-8 parts of titanium dioxide, 0.8-2 parts of sodium carboxymethylcellulose, 1-4 parts of zirconia and 2-5 parts of a red pigment;
the red pigment is iron oxide red.
6. The natural-like granite tile with antifouling effect as claimed in claim 1, wherein the brown particle suspension pulp is made of the following raw materials in parts by weight: 10-20 parts of mullite, 5-15 parts of kaolin, 5-10 parts of talc, 15-30 parts of albite, 5-15 parts of quartz powder, 6-10 parts of barium oxide, 4-8 parts of alumina, 3-8 parts of an antifouling material, 4-8 parts of titanium dioxide, 0.8-2 parts of sodium carboxymethylcellulose, 1-4 parts of zirconia and 2-5 parts of brown pigment;
the brown pigment is iron chromium brown.
7. The natural granite-like tile with an antifouling effect according to any one of claims 2 to 6, wherein the antifouling material is prepared by a method comprising: adding 0.5-2 parts of calcium carbonate, 0.5-2 parts of tin oxide and 0.8-2 parts of aluminum oxide into a mixer, uniformly mixing to obtain a mixture, adding the mixture into 0.5-3 wt% of phosphoric acid aqueous solution, stirring at the rotating speed of 60-150 rpm for 4-8 hours to obtain slurry, adding 1-4 parts of lanthanum nitrate into the slurry, stirring at the rotating speed of 60-150 rpm for 2-5 hours, filtering, drying, keeping the temperature in a muffle furnace at 450-600 ℃ for 2-5 hours, and grinding to 100-200 meshes to obtain the antifouling material.
8. The method for producing an antifouling imitated natural granite tile according to any of claims 1 to 6, comprising the steps of:
s1: preparing white particle suspension slurry, black particle suspension slurry, red particle suspension slurry and brown particle suspension slurry;
s2: mixing three or more than three kinds of suspension pulp of white particle suspension pulp, black particle suspension pulp, red particle suspension pulp and brown particle suspension pulp to obtain mixed pulp;
s3: spraying the mixed slurry on the surface of a ceramic tile blank with a smooth surface, and drying at 250-280 ℃ in a drying kiln;
s4: after drying, conveying the mixture to a roller kiln for sintering;
s5: and (3) edging the semi-finished brick by using conventional edging processing equipment to obtain the antifouling imitated natural granite ceramic tile.
9. The method for preparing an antifouling imitated natural granite ceramic tile according to claim 8, wherein the spraying amount in S3 is 500-700 ml/m2。
10. The method for producing an artificial natural granite ceramic tile having an antifouling effect according to claim 8, wherein the firing temperature in step S4 is 1150 to 1300 ℃ and the firing time is 60 to 90 min.
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