CN110746117B - Colored seeding glaze and positioning crystal ceramic tile prepared by using colored seeding glaze - Google Patents

Colored seeding glaze and positioning crystal ceramic tile prepared by using colored seeding glaze Download PDF

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CN110746117B
CN110746117B CN201911108852.1A CN201911108852A CN110746117B CN 110746117 B CN110746117 B CN 110746117B CN 201911108852 A CN201911108852 A CN 201911108852A CN 110746117 B CN110746117 B CN 110746117B
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glaze
seeding
colored
crystal
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CN110746117A (en
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谢志军
汪陇军
杨元东
王贤超
郑贵友
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Monalisa Group Co Ltd
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Monalisa Group Co Ltd
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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
    • C03C8/08—Frit compositions, i.e. in a powdered or comminuted form containing phosphorus
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C04B41/50—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
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C04B41/80—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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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Inorganic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Glass Compositions (AREA)

Abstract

The invention discloses a colored seeding glaze and a positioning crystal pattern ceramic tile prepared by using the colored seeding glaze. The colored seeding glaze comprises a basic glaze material and a wrapping pigment, wherein the basic glaze material comprises the following raw materials: by mass, 24-30% of potassium feldspar, 6-10% of albite, 10-14% of calcined kaolin, 3-5% of calcite, 1-3% of dolomite, 7-9% of barium carbonate and strontium carbonate: 3-5%, 5-7% of wollastonite, 1-3% of calcined talc, 2-4% of zinc oxide, and a seeding agent frit: 14-20%, tungsten oxide: 1-3%, calcium phosphate: 2-4%, tin oxide: 1 to 3 percent.

Description

Colored seeding glaze and positioning crystal ceramic tile prepared by using colored seeding glaze
Technical Field
The invention relates to a colored seeding glaze for positioning crystal ceramic tiles and a preparation method thereof, belonging to the technical field of ceramic tile production and manufacturing.
Background
In recent years, the production technology of architectural ceramics is rapidly developed, various new processes and new formulas are continuously applied, and the refinement and individuation of the decorative effect of the wall and floor tiles are urgent requirements for ceramic enterprises to realize product differentiation. The crystal fancy glaze is a high-grade artistic glaze with beautiful pattern effect formed on the glaze surface by separating out crystals in the glaze, has unique artistic decoration effect, has high ornamental value, is popular in the market, and is mainly applied to daily ceramics.
Chinese patent CN105565907B discloses a method for preparing a ceramic tile with crystal patterns of furnace transmutation and fixed color. The invention adopts the process of sequentially applying base coat, kiln-transmutation coat, positioning crystal-seeding coat and transparent protective coat on a plain brick blank, and the obtained brick blank is sintered to obtain the kiln-transmutation crystal-pattern crystal-seeding fixed-color ceramic brick. The process adopts a twice firing process, cannot combine a crystal pattern effect with a modern ink-jet printing technology, has a single glaze decoration effect, and cannot embody the texture effect of a modern ceramic tile. The invention introduces a large amount of calcium and magnesium chemical components, is not beneficial to color development of ceramic ink, and the whitening mechanism is that the glaze material is melted into frit and then separated out of willemite ZnO-SiO2Talc 3 MgO.4SiO2·H2The mixed opaque phase of O, quartz particles and variants improves the whiteness, but the use temperature is 1130 ℃, and the whitening effect in a brick kiln at the firing temperature of 1200 ℃ is greatly reduced.
Chinese patent CN103304277B discloses a microcrystalline glass ceramic composite board and a one-time fast sintering method thereof, wherein a large-crystal-pattern microcrystalline ceramic glass board with a composite crystal phase can be obtained by screen printing of seeding agent particles, then laying of microcrystalline glass particles, spraying of a fixing agent and sintering. The seeding agent adopting the process is frit fine particles, the seeding agent is colorless and transparent, the process cannot combine a crystal pattern effect with a modern ink-jet printing technology, the glaze decoration effect is single, and the texture effect of a modern ceramic tile cannot be reflected. The seeding agent is 30-mesh bright dry granular glaze, and boric acid, borax and other boron-containing components are introduced, and soda ash, potassium carbonate, sodium nitrate and other alkali metal fluxing agents with low initial melting points are introduced, so that the high-temperature viscosity of the seeding agent can be reduced, but the phenomena of large pores and more white spots are easily generated when the full-polishing process is adopted for polishing due to the low initial melting point.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a colored seeding glaze, a ceramic tile with oriented crystal pattern effect made by using the colored seeding glaze, and a preparation method thereof.
In a first aspect, the invention provides a colored seeding glaze, which comprises a base glaze material and a wrapping pigment, wherein the base glaze material comprises the following raw materials: by mass, 24-30% of potassium feldspar, 6-10% of albite, 10-14% of calcined kaolin, 3-5% of calcite, 1-3% of dolomite, 7-9% of barium carbonate and strontium carbonate: 3-5%, 5-7% of wollastonite, 1-3% of calcined talc, 2-4% of zinc oxide, and a seeding agent frit: 14-20%, tungsten oxide: 1-3%, calcium phosphate: 2-4%, tin oxide: 1-3%; wherein the chemical composition of the seeding agent frit comprises: SiO 22：60.5～64.5％、Al2O3：4.5～6.5％、Fe2O3：0～0.3％、TiO2：0～0.3％、CaO：0～0.5％、MgO：0～0.5％、K2O：5.0～7.0％、Na2O：4.5～5.5％、BaO：10.0～12.0％、P2O5: 0-0.5%, loss on ignition: 0.5 to 1.5 percent.
Preferably, the mass of the coating pigment is 3-8% of that of the basic glaze.
Preferably, the chemical composition of the base glaze comprises: by mass percent, SiO2：44.0～46.5％、Al2O3：11.5～14.0％、Fe2O3：0～0.2％、TiO2：0～0.2％、CaO：6.0～8.0％、MgO：0.5～2.0％、K2O：3.0～4.0％、Na2O：2.0～3.0％、BaO：7.0～9.0％、SrO：2～4％、ZnO：2.0～4.0％、P2O5：0.5～2.0％、WO3：1.0～3.0％、SnO2: 1.0-3.0%, loss on ignition: 5.5 to 6.5 percent.
In a second aspect, the present invention provides a ceramic tile made using any of the colored seeding glazes described above.
In a third aspect, the invention provides a method for preparing the ceramic tile, which comprises the following steps:
applying zirconium-free mutton tallow glaze on the blank, and then spraying ink to print a pattern;
positioning and applying a colored seeding glaze on the blank body printed with the patterns, and positioning and applying a crystal nucleus agent on the colored seeding glaze;
applying crystal flower dry grain glaze on the blank body coated with the crystal nucleus agent;
and sintering and polishing the blank body coated with the crystal flower dry grain glaze.
The colored seeding glaze is a semi-matte transparent glaze added with a seeding agent frit, and then a wrapping pigment is added to obtain the colored seeding glaze. The base glaze of the colored seeding glaze is semi-matte transparent glaze, and can promote the color development of the wrapping pigment and ensure the color development of the wrapping pigment to be bright. Meanwhile, the colored seeding glaze has low high-temperature viscosity, and seeding agent frit for promoting phase separation crystallization of the crystal nucleus agent is introduced, so that the crystal nucleus agent reacts with the colored seeding glaze printed at fixed points in a positioning way in the crystallization process, and the glaze surface is separated out colored crystal flowers with unique artistic effects. The glaze fired by the process can separate out beautiful colorless crystal flowers and colored crystal flowers with decoration effects, the polished effect gives people a bright visual impact feeling, and the grade of the ceramic tile glaze decoration effect can be effectively improved.
Preferably, the color seeding glaze is positioned and applied by adopting a roller printing mode.
More preferably, the colored seeding glaze in a dot shape and/or a line shape is positioned and applied by adopting a roller printing mode.
Preferably, the blank is subjected to glazing and then ink-jet printing to form a pattern.
Preferably, the glaze is a zirconium-free mutton tallow glaze.
More preferably, the raw materials of the zirconium-free mutton tallow glaze comprise: 45-55% of potassium feldspar, 15-25% of albite, 23-27% of kaolin and 3-7% of calcined alumina by mass percentage.
Preferably, the chemical composition of the zirconium-free mutton tallow glaze comprises: by mass percent, SiO2：59.0～64.0％、Al2O3：24.5～28.0％、Fe2O3：0～0.18％、TiO2：0～0.1％、CaO：0～0.5％、MgO：0～0.5％、K2O：4.5～6.0％、Na2O: 3.0-4.0%, loss on ignition: 3.0 to 4.5 percent.
The zirconium-free mutton tallow glaze is a matte glazeThe appearance of the semitransparent pure white glaze is pure white with sheepskin luster, and the semitransparent pure white glaze is fine and smooth in texture. The zirconium-free mutton tallow glaze does not contain zirconium silicate with high-temperature viscosity, so that the crystallization of crystal nucleating agent dry grains in crystal flower dry grain glaze can be effectively promoted, and meanwhile, the zirconium-free mutton tallow glaze does not contain zirconium so that SiO in the chemical composition of the formula2The content is relatively high, so that the ceramic ink has good and deep color development, and the fired glaze surface has fine and smooth texture and is mild, and the texture and the grade of the ceramic tile can be effectively improved.
Preferably, the raw materials of the crystal nucleus agent comprise: according to mass percent, potassium feldspar: 15-25%, albite: 5-15% of quartz: 10-14%, alumina: 0.5-1.5%, 14-18% of calcite, 8-12% of zinc oxide, fluorite: 1-3% of boric acid: 1-3%, calcium phosphate: 1-2% and rutile: 15-17% of zircon powder: 7-9%, tungsten oxide: 1 to 2 percent.
The crystal nucleus agent dry particles adopt rutile, zircon powder and the like as composite crystal nuclei, and crystal nucleus agents such as phosphate, fluoride and the like are introduced to promote phase separation and crystallization of silicate and phosphate. The crystal nucleus agent has high initial melting point of dry grains and wide sintering range, can well react with the low-viscosity crystal flower dry grain glaze, and promotes the glaze to separate out large crystal flowers with unique artistic effect.
Preferably, the chemical composition of the crystal nucleating agent comprises: by mass percent, SiO2：37～40.5％、Al2O3：5.5～7.0％、Fe2O3：0～0.2％、TiO2：16.0～18.0％、CaO：10.0～12.5％、MgO：0.1～0.5％、K2O：1.0～2.5％、Na2O：1.0～2.5％、ZnO：8.0～13.0％、F：0.5～1.5％、ZrO2：4.5～6.5％、P2O5：0.5～1.0％、B2O3：0.5～2.0％、WO3: 1.0-2.5%, loss on ignition: 1.0 to 2.0 percent.
Preferably, the raw materials of the crystal flower dry grain glaze comprise: 53-63% of potassium feldspar and quartz by mass percent: 10-14%, calcite: 11-15%, dolomite: 0-4%, zinc oxide: 10-12%, barium carbonate: 0-2%, strontium carbonate: 2-4%.
The crystal flower dry grain glaze has the advantages of high initial melting point, small high-temperature viscosity and wide sintering range, can well react with a crystal nucleus agent, promotes the glaze surface to separate out large crystal flowers, and is favorable for color development of ceramic ink. The glaze surface adopting the crystal flower dry grain glaze has good transparency, can effectively show the layering sense and the third dimension of the ceramic ink pattern, and the local position of the glaze surface can separate out beautiful crystal flower effect.
Preferably, the chemical composition of the crystal flower dry grain glaze comprises: by mass percent, SiO2：55.0～60.0％、Al2O3：9.0～11.0％、Fe2O3：0～0.15％、TiO2：0～0.1％、CaO：6.5～11.0％、MgO：0～1.5％、K2O：6.0～7.0％、Na2O: 0.5 to 1.5%, ZnO: 10.5-12.5%, BaO: 0-2.0%, SrO: 1.5-3.0%, loss on ignition: 0.5 to 1.0 percent.
According to the invention, the positioning crystal flower ceramic tile has a double-layer pattern effect, high-definition ink pattern layers are arranged under the glaze, and the colored crystal flowers with unique artistic effect are combined with the pattern layers of the white crystal flowers on the glaze.
Drawings
FIG. 1 is a flow chart illustrating the production of ceramic tiles according to one embodiment of the present invention.
FIG. 2 is a schematic diagram showing the structure of each layer of the ceramic tile according to one embodiment of the present invention, wherein "1" is a green body layer, "2" is a zirconium-free sheepskin glaze layer, "3" is an ink-jet pattern layer, "4" is a colored seeding glaze layer, "5" is a nucleating agent dry-grain glaze layer, and "6" is a crystal flower dry-grain glaze layer.
FIG. 3 is a photograph of the face of the ceramic tile made in example 1.
FIG. 4 is a photograph of the face of the tile made in example 2.
FIG. 5 is a photograph of the face of the tile made in example 3.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive. The following percentages are by mass unless otherwise specified.
The colored seeding glaze comprises a basic glaze material and a wrapping pigment, wherein the basic glaze material comprises the following raw materials: by mass, 24-30% of potassium feldspar, 6-10% of albite, 10-14% of calcined kaolin, 3-5% of calcite, 1-3% of dolomite, 7-9% of barium carbonate and strontium carbonate: 3-5%, 5-7% of wollastonite, 1-3% of calcined talc, 2-4% of zinc oxide, and a seeding agent frit: 14-20%, tungsten oxide: 1-3%, calcium phosphate: 2-4%, tin oxide: 1 to 3 percent.
Wherein, the chemical composition of the seeding agent frit comprises: SiO 22：60.5～64.5％、Al2O3：4.5～6.5％、Fe2O3：0～0.3％、TiO2：0～0.3％、CaO：0～0.5％、MgO：0～0.5％、K2O：5.0～7.0％、Na2O：4.5～5.5％、BaO：10.0～12.0％、P2O5: 0-0.5%, loss on ignition: 0.5 to 1.5 percent. The seeding agent frit is a low-aluminum high-silicon high-barium high-potassium sodium frit, a large amount of barium is introduced into the frit to improve the initial melting point, the high-temperature viscosity of the frit is small, the crystallization nucleating agent dry particle reaction is easy to separate out crystal flowers, and the seeding agent frit is usually used as a seeding agent material. In some embodiments, the chemical composition of the seeding agent frit comprises: SiO 22：62.4％、Al2O3：5.32％、Fe2O3：0.06％、TiO2：0.02％、CaO：0.21％、MgO：0.05％、K2O：6.03％、Na2O：5.23％、BaO：11.2％、P2O5: 0.22%, loss on ignition: 0.79 percent.
In some embodiments, the mass of the coating color is 3-8% of the mass of the base glaze. Preferably, the coating color is formed by coating a crystal nucleus agent on the outside of the coloring agent. In some embodiments, the encapsulated colorant is ZrSiO4/Cd(Sx,Se1-x). Wherein x is more than or equal to 0.1 and less than or equal to 1.0. When x is 0.1-0.4, package red; when x is 0.75-1.0, or coating yellow; when x is 0.5-0.65, the package is orange red.
The coating pigment is high-temperature resistant and stable ZrSiO4The crystal wraps the chromophoric substances CdS, CdSe and the like, and ZrSiO is formed outside the CdS and CdSe crystals4And the protective layer is formed into a wrapping pigment which is high temperature resistant to 1400 ℃ and stable in color development, and the highest using temperature of the common pigment is 1200-1300 ℃. The wrapping pigments are different in proportion with CdS and CdSe, so that all transition colors of red, orange and yellow are formed, the color generation intensity is high, and the color generation is bright and stable. The coating color can be coated red, coated yellow, coated orange, etc.
In some embodiments, the colored seeding glaze is prepared by weighing the raw materials according to the formula ratio, adding a proper amount of coating pigment, adding the binder and the debonder, adding water, and performing ball milling to obtain the colored seeding glaze.
The colored seeding glaze is a semi-matte transparent glaze added with a seeding agent frit, and pigments such as wrapping red, wrapping yellow and wrapping orange are respectively added to obtain the bright red, bright yellow and bright orange colored seeding glaze. The base glaze of the colored seeding glaze is semi-matte transparent glaze, and a certain amount of BaO, SrO and SnO is introduced2Not only can promote the color development of the coating pigment, but also can ensure the color development of the coating pigment to be bright. Meanwhile, the total amount of high-viscosity silicon and aluminum components in the colored seeding glaze is not high, and meanwhile, the high-temperature viscosity of the glaze can be greatly reduced by introducing more alkaline earth metal fluxing agents, particularly SrO, BaO, ZnO and other components into the chemical composition, the firing range is wider, and the color development of the coating pigment is promoted. Meanwhile, the colored seeding glaze is introduced with a low-temperature high-viscosity seeding agent frit for promoting the phase separation and crystallization of the following crystal nucleating agent dry particles, so that the CaF in the crystal nucleating agent dry particles2、P2O5、ZrSiO4、WO3、TiO2The components of the composite crystal nucleating agent and the inclusion material ZrSiO in the crystallization process4/Cd(Sx,Se1-x)、P2O5、WO3The colored seeding glaze of the crystal nucleus agent components react with each other in the high-temperature sintering process, so that colored crystal flowers with unique artistic effect are separated out from the glaze surface.
In some embodiments, the chemical composition of the base enamel includes: by mass percent, SiO2：44.0～46.5％、Al2O3：11.5～14.0％、Fe2O3：0～0.2％、TiO2：0～0.2％、CaO：6.0～8.0％、MgO：0.5～2.0％、K2O：3.0～4.0％、Na2O：2.0～3.0％、BaO：7.0～9.0％、SrO：2～4％、ZnO：2.0～4.0％、P2O5：0.5～2.0％、WO3：1.0～3.0％、SnO2: 1.0-3.0%, loss on ignition: 5.5 to 6.5 percent.
The colored seeding glaze of the invention is introduced with the wrapping pigment ZrSiO4/Cd(Sx,Se1-x) Wherein Cd (S)x,Se1-x) As the main component of the colorant, Cd (S) is wrapped at the same timex,Se1-x) ZrSiO of colorant4The crystal can also be used as a crystal nucleus agent, so the introduced coating pigment can be used as a coloring agent and also can be used as a crystal nucleus agent. Simultaneously introducing P into colored seeding glaze2O5、WO3The crystal nucleus agent can promote the colored introduced glaze to be easy to separate out crystal flowers in the high-temperature reaction process of the crystal nucleus agent dry particles. Simultaneously, a certain amount of SrO and BaO are introduced into the colored seeding glaze, especially SrO widens the firing temperature range and can promote the color development of the coating pigment, and a certain amount of SnO is introduced into the colored seeding glaze2The transparent glaze can have certain opaqueness, so that the encapsulated pigment can be promoted and developed, and the encapsulated pigment can be developed brightly.
The colored seeding glaze is semi-matte transparent raw glaze containing frits, a small amount of seeding agent frits are introduced to promote crystallization, and a wrapping pigment ZrSiO is also introduced to promote crystallization4/Cd(Sx,Se1-x)、P2O5、WO3The composite crystal nucleating agent is used for promoting crystallization, and SrO, ZnO and BaO are introduced to widen the sintering temperature range, and SnO is introduced2The color development of the coating pigment is promoted and the color development is bright. Meanwhile, the colored seeding glaze has a wider sintering range and less printing quantity, and can avoid the phenomena of large pores and more white spots during full polishing. The colored seeding glaze reacts with the crystal nucleus agent dry grains and the crystal flower dry grain glaze in the high-temperature sintering process, and the colored crystal flower is separated out while the white crystal flower is separated out.
The colored seeding glaze can be used for preparing ceramic tiles. FIG. 1 shows a process flow for ceramic tiles according to an embodiment of the present invention. FIG. 2 is a schematic view of the structure of the layers of the ceramic tile according to one embodiment of the present invention. The method for making the ceramic tile is described below with reference to FIGS. 1 and 2.
First, a green brick (or called a green body) is pressed to form a green body layer 1. The green body may be pressed from a ceramic matrix commonly used in the art.
The green body may then be dried. For example, the drying time is 50-75 min, and the moisture of the dried blank is controlled within 0.5%.
Then, optionally, a glaze, preferably a zirconium-free wool enamel, is applied to the blank to form a zirconium-free wool enamel layer 2. The zirconium-free mutton tallow glaze is a matte and semitransparent pure white glaze, the appearance of the glaze is pure white with mutton tallow gloss, and the glaze is fine and smooth in texture. By applying the zirconium-free mutton tallow glaze on the blank, the ground color of the blank can be covered, and the whiteness is improved.
In some embodiments, the raw materials of the zirconium-free mutton tallow glaze comprise: 45-55% of potassium feldspar (preferably water-washed ultra-white potassium feldspar), 15-25% of albite (preferably water-washed ultra-white albite), 23-27% of kaolin (preferably water-washed ultra-white kaolin) and 3-7% of calcined alumina. Preferably, the sum of the contents of the raw materials is 100%.
The chemical components of the zirconium-free mutton tallow glaze can comprise: SiO 22：59.0～64.0％、Al2O3：24.5～28.0％、Fe2O3：0～0.18％、TiO2：0～0.1％、CaO：0～0.5％、MgO：0～0.5％、K2O：4.5～6.0％、Na2O: 3.0-4.0%, loss on ignition: 3.0 to 4.5 percent.
In some embodiments, the zirconium-free mutton tallow glaze is prepared by weighing the raw materials according to a formula ratio, adding the binder and the debonding agent, simultaneously adding water, and performing ball milling to obtain glaze slip.
The zirconium-free mutton tallow glaze is low in iron content (less than or equal to 0.18 percent) and high in potassium content, and the glaze surface after firing is mild, white like jade, semi-transparent lard-like a coagulated mutton tallow, like a precious stone mutton tallow jade which is an excellent product in Hetian jade, so that the mutton tallow glaze is obtained. The surface of the fired mutton tallow glaze is smooth but not dazzling, and the glaze is low-gloss matte glaze, shows ivory white in the sun, and shines slightly yellow by strong light. The ultra-white potassium feldspar, the ultra-white albite, especially the ultra-white albite in the formula can increase the transparency of the mutton fat glaze, weaken the opacity of the mutton fat glaze and reduce the covering power of the mutton fat glaze, and the introduction of the high-white kaolin and the calcined alumina in the formula can reduce the transparency of the mutton fat glaze, increase the opacity of the mutton fat glaze and increase the covering power of the mutton fat glaze. The suet glaze formula adopts an ultra-white raw material with low iron content, so that the whiteness effect of common glaze and zirconium silicate can be achieved without using zirconium silicate.
The zirconium-free mutton tallow glaze is a pure white glaze with low gloss, matte and semitransparent, the appearance of the glaze is pure white with mutton tallow gloss, and the glaze is fine and smooth in texture and mild. The zirconium-free mutton tallow glaze does not contain zirconium silicate crystals with the highest high-temperature viscosity, so that the crystallization of the following crystal nucleating agent dry grains in the crystal flower dry grain glaze can be effectively promoted, and meanwhile, the zirconium-free mutton tallow glaze does not contain zirconium so as to cause SiO in the chemical composition of the formula2(59-64%) of the mutton tallow glaze is relatively high, and no calcium or magnesium chemical composition which is not beneficial to color development of the ceramic ink is introduced into the mutton tallow glaze, so that the ceramic ink has good color development and deep color development, the fired glaze surface has fine and smooth texture and is mild, and the texture and the grade of the ceramic tile can be effectively improved. The zirconium-free mutton tallow glaze is prepared by introducing materials with low iron and titanium contents such as ultra-white potassium, albite, ultra-white kaolin, calcined alumina and the like into the glaze, and Fe in the chemical composition2O3、TiO2The content is controlled to be Fe2O3：≤0.18％、TiO2: the glaze has a high whiteness degree within the range of not more than 0.1 percent, and meanwhile, the ultra-white kaolin and the calcined alumina are introduced to improve the opacity of the glaze, so that the covering power of the mutton tallow glaze is further improved, the whitening effect is achieved, and the whiteness degree after firing is 78-82 degrees. If chemical composition of Fe2O3、TiO2The content is higher, the whiteness after burning can be greatly reduced, and the whitening effect can not be achieved. The zirconium-free mutton tallow glaze has high whiteness after being burnt, and the whitening effect is improved by adding the super white kaolin and the calcined alumina to improve turbidity, so the zirconium-free mutton tallow glaze also has the opacifying whitening effect in a high-temperature roller kiln for producing floor tiles.
The zirconium-free mutton tallow glaze can be glazed by adopting a glaze spraying mode, and the glaze spraying technological parameters are as follows: a specific gravity of 1.40 to 1.50, preferably 1.44 to 1.46, and a weight of 450 to 550g/m2. The glaze spraying equipment can be a high-pressure water jet machine. The glaze adopting the glaze spraying technological parameters has better fluidity, good suspension property and difficult precipitation, and has good glaze spraying and atomizing effects and better smoothness of the sprayed glaze surface by using a high-pressure water jet machine.
Then, the inkjet design pattern was printed with a digital inkjet printer to form the inkjet pattern layer 3.
Then, a colored seeding glaze is applied on the inkjet pattern layer 3 to form a colored seeding glaze layer 4.
As shown in figure 2, the colored seeding glaze 4 is applied in a fixed-point positioning way, the application position of the colored seeding glaze corresponds to the application position of a crystal nucleating agent 5, and the crystal nucleating agent reacts with the colored seeding glaze applied in the fixed-point positioning way in the process of crystallization so that the glaze surface is separated out of colored crystal patterns with unique artistic effect. In some embodiments, the colored seeding glaze is applied by roll printing. The pattern range of the colored seeding glaze printed by the roller is consistent with the following glue pattern range (namely the following arrangement range of the crystal nucleating agent), and the fixed-point positioning of the colored crystal flower in the crystal flower area of the glaze surface is realized only by adopting a dot-shaped and/or linear pattern in the pattern of the colored seeding glaze printed by the roller. And after firing, the glaze surface precipitates beautiful crystal patterns at the positions distributed with the crystal nucleus agent, and colored crystal patterns with decoration effects are also arranged in the beautiful crystal pattern areas.
When the roller printing is carried out, the flow rate of the colored seeding glaze can be 15-25 seconds. The glaze flow rate was measured using a Shanghai Seiko LND-1 paint four paint cup viscometer. The main technological parameter of roller printing is the flow rate of glaze, and the flow rate of the glaze is too high, so that oil has poor fluidity, no glaze flows out of the roller, and colored seeding glaze cannot be printed; and the flow rate of the glaze is too low, the glaze has too good fluidity, and the printed pattern is fuzzy and has poor definition.
Then, a crystal nucleus agent dry grain glaze (crystal nucleus agent dry grain or crystal nucleus agent for short) is positioned and applied on the blank body to form a crystal nucleus agent dry grain glaze layer 5. As shown in FIG. 2, the crystal nucleator dry-grain glaze is at least partially applied to the locations where the colored seeding glaze is applied. The method for positioning and applying the crystal nucleus agent dry grain glaze can be as follows: the glue pattern is printed by a digital glue dry grain machine, the crystal nucleus agent dry grains are distributed by a distributing machine, and the redundant crystal nucleus agent dry grains which are not stuck by the glue are recycled.
The raw materials of the crystal nucleus agent may include: potassium feldspar: 15-25%, albite: 5-15% of quartz: 10-14%, alumina: 0.5-1.5%, 14-18% of calcite, 8-12% of zinc oxide, fluorite: 1-3% of boric acid: 1-3%, calcium phosphate: 1-2% and rutile: 15-17% of zircon powder: 7-9%, tungsten oxide: 1 to 2 percent. Preferably, the sum of the contents of the raw materials is 100%.
The crystal nucleus agent dry particles adopt fluorite, calcium phosphate, zircon powder, tungsten oxide and rutile as composite crystal nucleus agents, the raw materials of the crystal nucleus agents contain fluorite and calcium phosphate, and the crystal nucleus agents are easy to be used as crystal seeds to perform phase separation crystallization from silicate melts. P2O5Easily form asymmetric phosphate polyhedra in silica network, and P5+Field intensity greater than Si4+Therefore, it is easy to react with R+Or R2+And the silicon-oxygen network is separated from the silicon-oxygen network together, so that phase separation can be promoted, the interface energy is reduced, and the nucleation activation energy is reduced. Fluorite-introduced F-Can substitute O2-Without unduly affecting the arrangement of ions in the glass structure. But F-Is-1 valent, O2-Is-2 valent, so that there are only two F-By substitution of one O2-Electrical neutrality can be achieved. Reflected in a structure equivalent to the substitution of one siloxy bond (. ident.Si-O-Si. ident.) by two silicofluoride bonds (. ident.Si-F). The occurrence of Si-F group accelerates the breaking of silicon-oxygen network, leads to the weakening of glass structure, and can promote the nucleation of glass and induce the crystallization of glass. Fluorite and calcium phosphate are indispensable crystal nucleating agents in the crystal nucleating agent dry particles. The crystal nucleus agent is lack of fluorite in dry grains, and large crystal flowers which can be seen by naked eyes cannot be separated out by calcium phosphate.
The crystal nucleus agent can be obtained by mixing and melting the above raw materials into liquid glass, quenching with water, and processing into desired particle size. The grain size of the crystal nucleus agent can be 60-120 meshes, the dry grains with grain grading are high in stacking density, meanwhile, the fixing of the dry grain fixing agent is facilitated, the crystallization effect is not influenced, and the number of pores after polishing is small.
In one example, the raw materials are weighed according to the proportion, the raw materials are placed into a frit kiln to be melted into glass liquid at the temperature of 1500-1550 ℃, the glass liquid is quenched with water to obtain a nucleating agent frit, and the quenched frit is processed into 60-120 dry particles to obtain the nucleating agent.
The chemical composition of the crystal nucleating agent can comprise: SiO 22：37～40.5％、Al2O3：5.5～7.0％、Fe2O3：0～0.2％、TiO2：16.0～18.0％、CaO：10.0～12.5％、MgO：0.1～0.5％、K2O：1.0～2.5％、Na2O：1.0～2.5％、ZnO：8.0～13.0％、F：0.5～1.5％、ZrO2：4.5～6.5％、P2O5：0.5～1.0％、B2O3：0.5～2.0％、WO3: 1.0-2.5%, loss on ignition: 1.0 to 2.0 percent.
The amount of the nucleating agent can be 300-550 g/m2. By adopting the material distribution amount, the crystal flower precipitation effect after sintering is not influenced, and fewer pores after sintering and polishing can be ensured. The grain composition of the nucleating agent may be: 60-80 meshes: 15-25%, 80-100 mesh: 45-65%, 100-120 mesh: 25 to 35 percent. By adopting the grain grading, the dry grain fixing agent can bond more dry grains of the crystal nucleus agent under the condition that the gray level of the glue is not changed, and the effect of precipitating crystal flowers reaches the best effect.
Then, the crystal flower dry grain glaze of the present invention is applied to the entire surface of the body to form a crystal flower dry grain glaze layer 6. The crystal flower dry grain glaze can be applied by a common dry grain machine. The amount of the cloth can be 800-1000 g/m2. The glaze fired by the cloth amount has good flatness, the polished glaze has good transparency, the color development of ink is facilitated, the polished glaze has no obvious water ripple, and the texture of the glaze of the series of products can be improved. The grain composition of the crystal flower dry grain glaze can be as follows: 30-60 meshes: 20-30%, 60-80 mesh: 55-65%, 80-100 mesh: 20 to 25 percent. The dry grains with the grain composition have high bulk density, less pores after being sintered and polished, and no influence on the crystallization effect of the crystal nucleus agent. After the crystal flower dry grain glaze is applied, the crystal flower dry grain glaze is preferably fixed by a fixing agent (for example, a glue fixing agent sprayed by a high-pressure water jet machine). The specific gravity of the fixative may be 101-1.02, the application amount can be 250-300 g/m2。
The raw materials of the crystal flower dry grain glaze can comprise: 53-63% of potassium feldspar and quartz: 10-14%, calcite: 11-15%, dolomite: 0-4%, zinc oxide: 10-12%, barium carbonate: 0-2%, strontium carbonate: 2-4%. Preferably, the sum of the contents of the raw materials is 100%.
The chemical components of the crystal flower dry grain glaze can comprise: SiO 22：55.0～60.0％、Al2O3：9.0～11.0％、Fe2O3：0～0.15％、TiO2：0～0.1％、CaO：6.5～11.0％、MgO：0～1.5％、K2O：6.0～7.0％、Na2O: 0.5 to 1.5%, ZnO: 10.5-12.5%, BaO: 0-2.0%, SrO: 1.5-3.0%, loss on ignition: 0.5 to 1.0 percent. In some embodiments, the crystallized dry grain glaze is obtained by the following method: the raw materials are mixed according to a ratio and melted into glass liquid at the temperature of 1300-1400 ℃, and the glass liquid is processed into 30-100 mesh dry particles after water quenching.
The crystal flower dry grain glaze of the invention has high initial melting point, small high-temperature viscosity and wide sintering range, and the alkali metal flux in the formula is K2O as main component and very small amount of Na2O, so the crystal flower dry grain glaze has higher initial melting point and wider sintering range; meanwhile, the alkaline earth metal flux introduced into the formula mainly comprises barium carbonate, strontium carbonate, calcite, dolomite and zinc oxide, so that the high-temperature viscosity of the whole formula is reduced, particularly the introduction of BaO, SrO and ZnO can also widen the sintering temperature range of the formula, can well react with a crystal nucleating agent, promote the glaze surface to separate out large crystal flowers, and BaO, SrO and ZnO introduced into the dry grain glaze of the crystal flowers are beneficial to color development of ceramic ink. The crystal flower dry grain glaze introduces CaO, BaO, SrO and ZnO, so that the crystal flower dry grain has good transparency, the fired glaze surface has good transparency after polishing and good permeability, the layering and the stereoscopic impression of ceramic ink patterns can be effectively shown, and beautiful crystal flower effects are separated out at local positions of the glaze surface. Moreover, when the crystal dry grain glaze is coated, white crystal flowers with unique artistic effect are separated out. The ceramic tile adopting the crystal flower dry grain glaze embodies the details of the ink pattern texture and the white crystal flower effect completely, and after polishingThe ceramic tile gives a bright visual impact feeling to people and effectively improves the grade of the architectural ceramic glaze decoration effect.
And then drying, sintering, polishing and edging, and packaging in grades. The maximum sintering temperature can be 1190-1210 ℃, and the sintering period can be 100-150 minutes.
In one embodiment, after a layer of zirconium-free mutton tallow glaze is sprayed by a high-pressure water jet machine, an ink pattern is printed by a digital ink jet machine, a roller is used for printing a plurality of dot-shaped or linear colored seeding glazes, a digital glue grain drying machine is used for printing a digital glue pattern, a crystal nucleating agent grain drying machine is used for distributing a layer of crystal nucleating agent grains, a recovery system of the digital glue grain drying machine is used for sucking away crystal nucleating agent grains which are not stuck by glue under negative pressure for recycling, a layer of crystal flower grain drying glaze is distributed, the effect that colorless crystal flowers are separated out from fixed positions of the crystal nucleating agent in the crystal flower grain drying glaze is achieved, and meanwhile, the colored seeding glaze is printed in a fixed position in the range of the glue pattern through a roller, and the effect that colored crystal flowers are separated out from the fixed positions in the colorless crystal flower area is achieved.
The embodiment perfectly combines the ceramic building production processes of ink-jet printing, roller printing, a digital glue dry particle distribution system and the like, thereby realizing the fixed-point positioning of crystal flowers on the glaze surface of the ceramic tile and the fixed-point positioning of colored crystal flowers in the crystal flower area of the glaze surface, successfully applying the crystal flower glaze with unique artistic effect to the architectural ceramic decorative material, and enriching the decorative effect of the architectural ceramic glaze surface. The glazed tile produced by the process has double-layer pattern effect, high-definition ink pattern layers are arranged under the glaze, and the pattern layers with unique artistic effect and colored crystal flowers combined with colorless crystal flowers are arranged on the glaze.
In one embodiment, after a layer of zirconium-free mutton tallow glaze is sprayed on a dried blank by a high-pressure water jet machine, an ink pattern is printed by a digital ink jet machine, a colored seeding glaze is printed at fixed points and positioned by a roller printer, a glue pattern is printed by a digital glue drying granulator, crystal nucleating agent dry granules are distributed by a distributing machine, redundant crystal nucleating agent which is not stuck by glue is recycled by a negative pressure system, a layer of crystal flower dry granule glaze is distributed by a common drying granulator, a glue fixing agent is sprayed by the high-pressure water jet machine, the crystal flower dry granules are dried by a drying kiln and then sintered, and the crystal flower dry granules are polished and packaged in a grading manner.
The pattern range of the colored seeding glaze printed by the roller is consistent with the glue pattern range of the glue grain drying machine, and the fixed-point positioning of the colored crystal patterns in the crystal pattern area of the glaze surface is realized only by adopting dot-shaped or linear patterns for the pattern of the colored seeding glaze printed by the roller. And after firing, the glaze surface precipitates beautiful crystal patterns at the positions distributed with the crystal nucleus agent, and colored crystal patterns with decoration effects are also arranged in the beautiful crystal pattern areas.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
The method comprises the following steps: and pressing the green brick. The green body is pressed from a ceramic base material commonly used in the art.
Step two: drying the blank for 60min, and controlling the moisture of the dried blank within 0.5%.
Step three: spraying zirconium-free mutton tallow glaze on the dried green bricks in a glaze spraying mode, wherein the zirconium-free mutton tallow glaze comprises the following raw materials: 50% of water-washed ultra-white potassium feldspar, 20% of water-washed ultra-white albite, 25% of water-washed ultra-white kaolin and 5% of calcined alumina. The zirconium-free mutton tallow glaze comprises the following chemical components: SiO 22：60.92％、Al2O3：26.08％、Fe2O3：0.11％、TiO2：0.01％、CaO：0.21％、MgO：0.09％、K2O：5.03％、Na2O: 3.59%, loss on ignition: 3.96 percent. The specific gravity of the glaze material is 1.45, and the glaze spraying amount is 480g/m2。
Step four: the ink-jet design pattern was printed with a digital ink-jet printer.
Step five: and printing the colored seeding glaze by using a roller engraved with an effect pattern. The colored seeding glaze comprises a baseGlaze and wrapping red pigment. The basic glaze comprises the following raw materials: 30% of potassium feldspar, 6% of albite, 10% of calcined kaolin, 3% of calcite, 3% of dolomite, 8% of barium carbonate, and 8% of strontium carbonate: 5%, wollastonite 7%, calcined talc 3%, zinc oxide 4%, seeding agent frit: 14%, tungsten oxide: 1%, tin oxide: 2%, calcium phosphate: 4 percent. The chemical composition of the basic glaze material is as follows: SiO 22：44.15％、Al2O3：11.81％、Fe2O3：0.1％、TiO2：0.06％、CaO：7.94％、MgO：1.77％、K2O：3.80％、Na2O：2.36％、BaO：7.77％、SrO：3.51％、ZnO：3.98％，P2O5：1.81％，WO3：1.01％，SnO2: 1.99%, loss on ignition: 6.49 percent. The coating red pigment comprises ZrSiO4/Cd(S0.3,Se0.7). Wherein, the mass of the wrapping red pigment is 5 percent of that of the basic glaze. Frit flow rate 20 seconds.
Step six: printing a glue pattern by using a digital glue dry granulation machine, distributing a layer of crystal nucleus agent dry granules by using the digital glue dry granulation machine, and simultaneously pumping out the crystal nucleus agent dry granules which are not stuck by the glue by using a recovery system under negative pressure for cyclic utilization. The crystal nucleus agent comprises the following raw materials: potassium feldspar: 15%, albite: 15%, quartz: 10%, alumina: 0.5%, calcite 18%, zinc oxide 12%, fluorite: 1%, boric acid: 1%, calcium phosphate: 2%, rutile: 15.5%, zircon powder: 9%, tungsten oxide: 1 percent. Weighing the raw materials according to the proportion, melting the raw materials into liquid glass at the temperature of 1525 ℃, quenching the glass liquid to obtain a nucleating agent frit, and processing the water-quenched frit into 60-120-mesh dry particles for later use. The chemical composition of the crystal nucleating agent is as follows: SiO 22：37.33％、Al2O3：5.92％、Fe2O3：0.09％、TiO2：16.47％、CaO：12.29％、MgO：0.31％、K2O：1.51％、Na2O：2.04％、ZnO：12.74％、F：0.51％、ZrO2：6.22％、P2O5：0.97％、B2O3：0.59％、WO3: 1.06%, loss on ignition: 1.83 percent. Of dry particles of nucleating agentsThe cloth amount was 400g/m2. And (3) dry particle size grading of the crystal nucleating agent: 60-80 meshes: 18.8%, 80-100 mesh: 49.7%, 100-120 mesh: 31.5 percent.
Step seven: distributing a layer of crystal flower dry grain glaze by using a common dry grain machine, wherein the crystal flower dry grain glaze comprises the following raw materials: 58% of potassium feldspar, and quartz: 12%, calcite: 13%, dolomite: 2%, barium carbonate: 1%, strontium carbonate: 3%, zinc oxide: 11 percent. . Weighing the raw materials according to the proportion, putting the raw materials into a frit kiln to be melted into liquid glass at the temperature of 1350 ℃, performing water quenching on the glass liquid to obtain crystal flower frit, and processing the water-quenched frit into dry particles of 30-100 meshes for later use. The chemical composition of the crystal flower dry grain glaze is as follows: SiO 22：56.27％、Al2O3：9.96％、Fe2O3：0.11％、TiO2：0.02％、CaO：8.82％、MgO：0.64％、K2O：6.43％、Na2O: 1.39%, BaO: 0.83%, SrO: 2.25%, ZnO: 11.70%, loss on ignition: 0.75 percent. The distribution amount of the crystal flower dry grain glaze is 900g/m2。
Step eight: and (4) fixing the dried cloth particles by using a glue fixing agent sprayed by a high-pressure water jet machine. The specific gravity of the fixing agent is 1.01, and the application amount is 280g/m2。
Step nine: the glaze blank sprayed with the glue is dried by a glaze line drying kiln and then quickly fired by a roller kiln. The maximum firing temperature is 1210 ℃, and the firing period is 110 min.
Step ten: and polishing and edging the fired brick, and packaging in a grading manner.
FIG. 3 is a photograph of the surface of the ceramic tile produced in example 1, which shows that the surface of the ceramic tile has not only bright stone texture patterns, but also some white fixed-point positioned stereoscopic crystal flower effect pattern layers, and the white crystal flower patterns also have colored crystal flowers.
The abrasion resistance of the glaze surface is tested by adopting a test method in GB/T3810.7-2016 (determination of surface abrasion resistance of glazed bricks), the pollution resistance of the glaze surface is tested by adopting a test method in GB/T3810.14-2016 (determination of pollution resistance), and the glossiness of the glaze surface is tested by adopting a test method in GB/T13891-.
The ceramic tile glaze obtained in example 1 has an abrasion resistance of 1500 rpm, a level of 3, a stain resistance level of 3, and a gloss of 91-95 degrees after polishing.
Example 2
The difference from example 1 is that: the colored seeding glaze comprises a base glaze material and a wrapping orange red material. The basic glaze comprises the following raw materials: 24% of potassium feldspar, 10% of albite, 14% of calcined kaolin, 5% of calcite, 1% of dolomite, 7% of barium carbonate, and the weight ratio of strontium carbonate: 4%, wollastonite 5%, calcined talc 1%, zinc oxide 2%, seeding agent frit: 20%, tungsten oxide: 2%, tin oxide: 3%, calcium phosphate: 2 percent. The chemical composition of the basic glaze material is as follows: SiO 22：46.37％、Al2O3：13.64％、Fe2O3：0.1％、TiO2：0.07％、CaO：6.47％、MgO：0.71％、K2O：3.60％、Na2O：2.83％、BaO：7.67％、SrO：2.80％、ZnO：2.01％，P2O5：0.91％，WO3：1.99％，SnO2: 2.99%, loss on ignition: 5.86 percent. The orange red coating comprises ZrSiO4/Cd(S0.6,Se0.4). Wherein, the mass of the coating orange red pigment is 8 percent of that of the basic glaze.
Fig. 4 is a photograph of the surface of the ceramic tile manufactured in example 2, which shows that the surface of the ceramic tile has not only the bright stone texture pattern but also some white fixed-point positioned stereoscopic crystal flower effect pattern layers, and the white crystal flower pattern also has colored crystal flowers.
The abrasion resistance of the glaze surface is tested by adopting a test method in GB/T3810.7-2016 (determination of surface abrasion resistance of glazed bricks), the pollution resistance of the glaze surface is tested by adopting a test method in GB/T3810.14-2016 (determination of pollution resistance), and the glossiness of the glaze surface is tested by adopting a test method in GB/T13891-.
The ceramic tile glaze obtained in example 2 has abrasion resistance of 1500 turns, 3 grades, stain resistance of 4 grades and glossiness of 93-97 degrees after polishing.
Example 3
Different from that of embodiment 1The method is characterized in that: the colored seeding glaze comprises a base glaze material and a wrapping yellow material. The basic glaze comprises the following raw materials: 27% of potassium feldspar, 8% of albite, 12% of calcined kaolin, 4% of calcite, 2% of dolomite, 9% of barium carbonate, and 9% of strontium carbonate: 3%, wollastonite 6%, calcined talc 2%, zinc oxide 3%, seeding agent frit: 17%, tungsten oxide: 3%, tin oxide: 1%, calcium phosphate: 3 percent. The chemical composition of the basic glaze material is as follows: SiO 22：45.26％、Al2O3：12.72％、Fe2O3：0.1％、TiO2：0.07％、CaO：7.20％、MgO：1.24％、K2O：3.70％、Na2O：2.60％、BaO：8.88％、SrO：2.10％、ZnO：2.99％，P2O5：1.36％，WO3：2.99％，SnO2: 1.01%, loss on ignition: 6.08 percent. The coating yellow pigment has the chemical composition of ZrSiO4/Cd(S0.9,Se0.1). Wherein the mass of the wrapping yellow pigment is 3% of that of the basic glaze.
FIG. 5 is a photograph of the surface of the ceramic tile produced in example 3, which shows that the surface of the ceramic tile has not only the colorful stone texture pattern, but also some white fixed-point positioned stereoscopic crystal pattern layers, and the white crystal pattern also has colored crystal flowers.
The abrasion resistance of the glaze surface is tested by adopting a test method in GB/T3810.7-2016 (determination of surface abrasion resistance of glazed bricks), the pollution resistance of the glaze surface is tested by adopting a test method in GB/T3810.14-2016 (determination of pollution resistance), and the glossiness of the glaze surface is tested by adopting a test method in GB/T13891-.
The ceramic tile glaze obtained in example 3 has an abrasion resistance of 1500 rpm, a level of 3, a stain resistance level of 3, and a gloss of 92-96 degrees after polishing.

Claims (14)

1. The colored seeding glaze is characterized by comprising a basic glaze material and a wrapping pigment, wherein the basic glaze material comprises the following raw materials: by mass, 24-30% of potassium feldspar, 6-10% of albite, 10-14% of calcined kaolin, 3-5% of calcite, 1-3% of dolomite, 7-9% of barium carbonate and strontium carbonate:3-5%, 5-7% of wollastonite, 1-3% of calcined talc, 2-4% of zinc oxide, and a seeding agent frit: 14-20%, tungsten oxide: 1-3%, calcium phosphate: 2-4%, tin oxide: 1-3%; wherein the chemical composition of the seeding agent frit comprises: by mass percent, SiO2：60.5～64.5%、Al2O3：4.5～6.5%、Fe2O3：0～0.3%、TiO2：0～0.3%、CaO：0～0.5%、MgO：0～0.5%、K2O：5.0～7.0%、Na2O：4.5～5.5%、BaO：10.0～12.0%、P2O5: 0-0.5%, loss on ignition: 0.5 to 1.5 percent.
2. The colored seeding glaze according to claim 1, wherein the mass of the coating color is 3-8% of that of the base glaze.
3. The colored seeding glaze according to claim 1, wherein the chemical composition of the base glaze material comprises: by mass percent, SiO2：44.0～46.5%、Al2O3：11.5～14.0%、Fe2O3：0～0.2%、TiO2：0～0.2%、CaO：6.0～8.0%、MgO：0.5～2.0%、K2O：3.0～4.0%、Na2O：2.0～3.0%、BaO：7.0～9.0%、SrO：2～4%、ZnO：2.0～4.0%、P2O5：0.5～2.0%、WO3：1.0～3.0%、SnO2: 1.0-3.0%, loss on ignition: 5.5 to 6.5 percent.
4. A ceramic tile made using the colored seeding glaze of any one of claims 1 to 3.
5. A method for making the ceramic tile of claim 4, comprising the steps of:
printing a pattern on the blank by ink jet;
positioning and applying a colored seeding glaze on the blank body printed with the patterns, and positioning and applying a crystal nucleus agent on the colored seeding glaze;
applying crystal flower dry grain glaze on the blank body coated with the crystal nucleus agent;
and sintering and polishing the blank body coated with the crystal flower dry grain glaze.
6. The preparation method according to claim 5, characterized in that the color seeding glaze is positioned and applied by a roller printing mode.
7. The preparation method according to claim 6, characterized in that the colored seeding glaze in dot and/or line shape is positioned and applied by a roller printing mode.
8. The method according to claim 5, wherein the blank is subjected to glazing and then ink-jet printing of a pattern; the glaze is zirconium-free mutton tallow glaze.
9. The preparation method according to claim 8, wherein the zirconium-free mutton tallow glaze comprises the following raw materials: 45-55% of potassium feldspar, 15-25% of albite, 23-27% of kaolin and 3-7% of calcined alumina by mass percentage.
10. The preparation method according to claim 9, wherein the chemical composition of the zirconium-free mutton tallow glaze comprises: by mass percent, SiO2：59.0～64.0%、Al2O3：24.5～28.0%、Fe2O3：0～0.18%、TiO2：0～0.1%、CaO：0～0.5%、MgO：0～0.5%、K2O：4.5～6.0%、Na2O: 3.0-4.0%, loss on ignition: 3.0 to 4.5 percent.
11. The method according to claim 5, wherein the raw materials of the crystal nucleus agent include: according to mass percent, potassium feldspar: 15-25%, albite: 5-15% of quartz: 10-14%, alumina: 0.5-1.5%, 14-18% of calcite, 8-12% of zinc oxide, fluorite: 1-3% of boric acid: 1-3%, calcium phosphate: 1-2% and rutile: 15-17% of zircon powder: 7-9%, tungsten oxide: 1 to 2 percent.
12. The method of claim 11, wherein the chemical composition of the crystal nucleating agent comprises: by mass percent, SiO2：37～40.5%、Al2O3：5.5～7.0%、Fe2O3：0～0.2%、TiO2：16.0～18.0%、CaO：10.0～12.5%、MgO：0.1～0.5%、K2O：1.0～2.5%、Na2O：1.0～2.5%、ZnO：8.0～13.0%、F：0.5～1.5%、ZrO2：4.5～6.5%、P2O5：0.5～1.0%、B2O3：0.5～2.0%、WO3: 1.0-2.5%, loss on ignition: 1.0 to 2.0 percent.
13. The preparation method according to claim 5, wherein the raw materials of the crystal flower dry grain glaze comprise: 53-63% of potassium feldspar and quartz by mass percent: 10-14% and calcite: 11-15% of dolomite: 0-4%, zinc oxide: 10-12% and barium carbonate: 0-2%, strontium carbonate: 2-4%.
14. The preparation method according to claim 13, wherein the chemical composition of the crystal flower dry grain glaze comprises: by mass percent, SiO2：55.0～60.0%、Al2O3：9.0～11.0%、Fe2O3：0～0.15%、TiO2：0～0.1%、CaO：6.5～11.0%、MgO：0～1.5%、K2O：6.0～7.0%、Na2O: 0.5 to 1.5%, ZnO: 10.5-12.5%, BaO: 0-2.0%, SrO: 1.5-3.0%, loss on ignition: 0.5 to 1.0 percent.
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6174608B1 (en) * 1997-11-27 2001-01-16 Ferro (Italia) Srl Ceramic tile and glaze for use thereon
JP2010202434A (en) * 2009-03-02 2010-09-16 Nippon Electric Glass Co Ltd Colored crystallized glass article and method for manufacturing the same
WO2011108472A1 (en) * 2010-03-01 2011-09-09 株式会社 オハラ Glass for glaze, glaze, and photocatalyst member
CN103833419A (en) * 2014-01-02 2014-06-04 惠达卫浴股份有限公司 Purple bronze glaze with metallic luster and preparation method thereof
CN104193411A (en) * 2014-08-05 2014-12-10 广东道氏技术股份有限公司 Crystalline glaze for sanitary ceramic sanitary ware and preparation process thereof
CN104311155A (en) * 2014-10-11 2015-01-28 杭州诺贝尔陶瓷有限公司 Crystal glaze ceramic tile and production method thereof
CN108129027A (en) * 2018-01-30 2018-06-08 广东宏海陶瓷实业发展有限公司 There are the crystallization glazed tile of friable mica effect, parent glaze and preparation method thereof in surface
CN109455934A (en) * 2018-12-19 2019-03-12 蒙娜丽莎集团股份有限公司 Color decorative effect Ceramic Tiles of a kind of stream and preparation method thereof
CN109455933A (en) * 2018-12-19 2019-03-12 蒙娜丽莎集团股份有限公司 A kind of crystalline glaze and use Ceramic Tiles made from the crystalline glaze

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6174608B1 (en) * 1997-11-27 2001-01-16 Ferro (Italia) Srl Ceramic tile and glaze for use thereon
JP2010202434A (en) * 2009-03-02 2010-09-16 Nippon Electric Glass Co Ltd Colored crystallized glass article and method for manufacturing the same
WO2011108472A1 (en) * 2010-03-01 2011-09-09 株式会社 オハラ Glass for glaze, glaze, and photocatalyst member
CN103833419A (en) * 2014-01-02 2014-06-04 惠达卫浴股份有限公司 Purple bronze glaze with metallic luster and preparation method thereof
CN104193411A (en) * 2014-08-05 2014-12-10 广东道氏技术股份有限公司 Crystalline glaze for sanitary ceramic sanitary ware and preparation process thereof
CN104311155A (en) * 2014-10-11 2015-01-28 杭州诺贝尔陶瓷有限公司 Crystal glaze ceramic tile and production method thereof
CN108129027A (en) * 2018-01-30 2018-06-08 广东宏海陶瓷实业发展有限公司 There are the crystallization glazed tile of friable mica effect, parent glaze and preparation method thereof in surface
CN109455934A (en) * 2018-12-19 2019-03-12 蒙娜丽莎集团股份有限公司 Color decorative effect Ceramic Tiles of a kind of stream and preparation method thereof
CN109455933A (en) * 2018-12-19 2019-03-12 蒙娜丽莎集团股份有限公司 A kind of crystalline glaze and use Ceramic Tiles made from the crystalline glaze

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Reduction of maturation point in crystalline glaze through frit addition;Niti Yongvanich et al.;《Monatshefte Fur Chemie》;20170601;第148卷;第1329-1335页 *
熔块的配制及其在结晶釉中的应用;拉赫曼;《装饰》;20041231(第5期);第94页 *
铁红结晶釉的制备;包启富;《砖瓦》;20161231(第12期);第10-11页 *

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