CN110903033A - Crystal nucleating agent and positioning crystal pattern ceramic tile prepared by using same - Google Patents

Crystal nucleating agent and positioning crystal pattern ceramic tile prepared by using same Download PDF

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Publication number
CN110903033A
CN110903033A CN201911107584.1A CN201911107584A CN110903033A CN 110903033 A CN110903033 A CN 110903033A CN 201911107584 A CN201911107584 A CN 201911107584A CN 110903033 A CN110903033 A CN 110903033A
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crystal
glaze
crystal nucleus
nucleus agent
percent
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CN110903033B (en
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萧礼标
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
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • 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
    • 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
    • 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

Abstract

The invention discloses a crystal nucleating agent and a positioning crystal pattern ceramic tile prepared by using the crystal nucleating agent. The crystal nucleus agent comprises the following raw materials: 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.

Description

Crystal nucleating agent and positioning crystal pattern ceramic tile prepared by using same
Technical Field
The invention relates to a crystal nucleating agent for positioning crystal flower ceramic tiles and a using 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 CN 104311155A discloses a crystallized glaze ceramic tile and a production method thereof, wherein crystallized frits and seed crystals are applied on a conventional porcelain tile blank, the temperature is raised to 1130-1200 ℃, the temperature is kept for 10-30 min, then the temperature is lowered to 1000-1080 ℃, the temperature is kept for 1-2 h at the temperature, and the crystallized glaze ceramic tile with obvious crystal flower effect is prepared. The crystal pattern brick produced by the process has long sintering time and harsh sintering conditions, is difficult to produce in batch under the current sintering system condition of the building ceramic, and has high production cost. The crystal nucleus agent only contains a trace (0.2-0.8%) of titanium crystal nucleus agent component, and the formed crystal phase is CaO & TiO2And SrTiO3。
Chinese patent CN102936156A discloses a glaze material of a high-temperature fast-fired crystal glaze archaized brick and a preparation process thereof. The process adopts the steps of spraying the crystallized colored base glaze, then printing the crystallizing agent frit dry particles through a screen, and then adopting screen printing to quickly fire the transparent or colored dry particles in a roller kiln to obtain the antique brick with the crystal pattern effect in different colors. The invention introduces a large amount of lithium carbonate and soda ash with low initial melting point and strong fluxing, and the titanium and zirconium crystal nucleating agent components are introduced, but the low initial melting point material can only be applied to the crystal glaze effect of the natural surface.
Disclosure of Invention
In view of the above problems, the present invention provides a crystallization nucleator, a ceramic tile with oriented crystal pattern effect manufactured by using the crystallization nucleator, and a manufacturing method thereof.
In a first aspect, the present invention provides a crystal nucleating agent, wherein the crystal nucleating agent comprises the following raw materials: 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.
Preferably, the crystal nucleus agent is obtained by the following method: the raw materials are mixed according to a ratio and melted into glass liquid at the temperature of 1500-1550 ℃, and the glass liquid is processed into 60-120 mesh dry particles after water quenching.
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.
The crystal nucleus agent dry particles adopt rutile and zircon powder as composite crystal nuclei, and phosphate and fluoride 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 dry grain glaze of crystal flowers, and promotes the glaze to separate out large crystal flowers with unique artistic effects. Moreover, the crystal nucleus agent has higher initial melting point, does not contain strong fluxing flux with low initial melting point such as soda ash, lithium carbonate and the like, introduces zinc oxide with high initial melting point, a small amount of fluorite and boric acid as fluxing agents, simultaneously introduces components such as fluorine, phosphorus and the like to promote crystallization of zirconium, titanium and tungsten crystal nucleus agents in the crystal flower dry grain glaze, and the positioning crystal flower ceramic tile adopting the process is a glazed tile of a full-polishing process, but a crystal glaze tile of an unnatural surface, and can be produced in batches under the current quick firing process condition of building ceramics.
In a second aspect, the present invention provides a ceramic tile made using any of the above nucleating agents.
In a third aspect, the invention provides a method for preparing the ceramic tile, which comprises the following steps:
printing a pattern on the blank by ink jet;
positioning and applying the crystal nucleus agent on the blank body printed with the pattern;
applying crystal flower dry grain glaze on the blank body coated with the crystal nucleus agent;
and sintering the blank body coated with the crystal flower dry grain glaze, and polishing by adopting a full polishing process.
Preferably, the blank is subjected to glazing and then ink-jet printing to form a pattern.
Preferably, the glaze is an inkjet pigmented glaze.
More preferably, the raw materials of the inkjet coloring glaze comprise: according to mass percent, potassium feldspar: 33-45%, albite: 15-25% of kaolin: 22-27% of calcined alumina: 5-9%, zirconium silicate: 8-10%.
Preferably, the chemical composition of the inkjet coloring glaze comprises: by mass percent, SiO2：55.0～60.0％、Al2O3：23.5～25.5％、Fe2O3：0～0.5％、TiO2：0～0.1％、CaO：0～0.5％、MgO：0～0.3％、K2O：4.0～5.5％、Na2O：2.0～3.5％、ZrO2: 8.0-12.0%, loss on ignition: 3.0 to 4.5 percent.
The ink-jet coloring glaze is a matte zirconium opaque white glaze, calcium and magnesium fluxing agents are not introduced into the ink-jet coloring glaze, the coloring of ceramic ink is facilitated, the firing range of the ink-jet coloring glaze is wide, the ink-jet coloring glaze is well combined with crystal flower dry particle glaze, pores are few after the ink-jet coloring glaze is polished by a full polishing process, and the texture and the grade of a ceramic tile can be effectively improved.
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 positioning crystal flower pattern layers with unique artistic effects are arranged 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 an inkjet coloring glaze layer, "3" is an inkjet pattern layer, "4" is a crystal nucleus agent dry grain glaze layer, and "5" 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.
FIG. 6 is a photograph of the tile face of the ceramic tile made in comparative example 1.
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 crystal nucleus agent (also called crystal nucleus agent dry grain glaze or crystal nucleus agent dry grain) of one embodiment of the invention comprises the following raw materials: 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 chemical composition of the crystal nucleator may include: 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.
The raw material of the crystal nucleus agent contains fluorite and calcium phosphate, wherein the fluorite, the calcium phosphate, the zircon powder, the tungsten oxide and the rutile are introduced as the composite crystal nucleus agent and are easy to phase separate from the silicate melt. 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 groups accelerates the formation of silicon-oxygen networkThe breakage of the complex leads to the weakening of the glass structure, can promote the nucleation of the glass and induce the crystallization of the 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 invention does not use potassium carbonate and sodium carbonate components with low initial melting points and lead components with toxicity and no environmental protection, and does not need to form crystallization effect by virtue of temperature difference between crystallization crystal grains and base glaze. In addition, the invention does not introduce a lithium component with low initial melting point and strong fluxing, so that the initial melting point of the crystal nucleus agent dry particles is higher, except introducing titanium and zirconium crystal nucleus agent components, phosphorus, fluorine, tungsten and other crystal nucleus agent components are also introduced, and the crystal nucleus agent dry particles with high initial melting point are easy to react and separate out the crystal flower dry particle glaze and the ceramic tile with the crystal flower positioning effect by adopting the full-polishing process.
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, 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-mesh dry particles for later use.
The crystal nucleating agent 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 water content of the dried blank is controlled within 0.5%.
Then, optionally, an inkjet coloring glaze layer 2 is formed by applying glaze, preferably inkjet coloring glaze, on the green body. The ink-jet coloring glaze is a matte zirconium opaque white glaze, calcium and magnesium fluxing agents are not introduced into the ink-jet coloring glaze, the coloring of ceramic ink is facilitated, the firing range of the ink-jet coloring glaze is wide, the ink-jet coloring glaze is well combined with crystal flower dry particle glaze, pores are few after the ink-jet coloring glaze is polished by a full polishing process, and the texture and the grade of a ceramic tile can be effectively improved. By applying the ink-jet coloring glaze on the blank, the ground color of the blank can be covered, and the whiteness is improved.
In some embodiments, the inkjet colored glaze comprises the following raw materials: potassium feldspar: 33-45%, albite: 15-25% of kaolin: 22-27% of calcined alumina: 5-9%, zirconium silicate: 8-10%. Preferably, the sum of the contents of the raw materials is 100%.
The chemical composition of the inkjet coloring glaze may include: SiO 22：55.0～60.0％、Al2O3：23.5～25.5％、Fe2O3：0～0.5％、TiO2：0～0.1％、CaO：0～0.5％、MgO：0～0.3％、K2O：4.0～5.5％、Na2O：2.0～3.5％、ZrO2: 8.0-12.0%, loss on ignition: 3.0 to 4.5 percent.
In some embodiments, the inkjet coloring 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 the inkjet coloring glaze.
The inkjet coloring 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/m2The 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.
Next, a crystal nucleus agent dry grain glaze (referred to as crystal nucleus agent dry grain or crystal nucleus agent for short) is positioned and applied on the blank after the ink-jet printing to form a crystal nucleus agent dry grain glaze layer 4, as shown in fig. 2. 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.
As described above, 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 rutile, zircon powder and tungsten oxide as composite crystal nuclei, and phosphate and fluoride (fluorite) 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, and can well react with the crystal flower dry grain glaze. The crystal nucleus agent uses TiO as dry particles2、ZrSiO4、WO3、P2O5F, etc. of a composite crystal nucleus, ZrSiO4The solubility in silicate melts is low, typically exceeding 3%, making it difficult to dissolve and tending to precipitate zirconium oxygen-rich crystals from the melt, thereby promoting glass melt nucleation. TiO 22It is easy to separate (separate) from the silica network together with other RO type oxides, and on the basis of this, forms crystal nuclei to promote glass crystallization. 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. The introduction of the F element accelerates the fracture of a silica network, can promote glass nucleation, promotes glass nucleation and induces glass crystallization. WO3The melting point is higher, the degree of fusion is smaller in silicate glass phase and low-alkali borate glass phase, the invention is mainly used for promoting crystallization of crystalline glaze and microcrystalline glass, and a certain amount of WO is introduced into the invention3Can promote TiO2、ZrSiO4、P2O5Nucleating agents such as F in siliconThe crystallization of the acid salt glass phase promotes the glaze surface to separate out large crystal patterns with unique artistic effect.
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 nucleator may include: 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.
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 green body to form a crystal flower dry grain glaze layer 5. 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, and the polished glaze is polishedThe glaze surface has no obvious water wave, and the glaze texture 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 grain grading crystal flower dry grains have high bulk density, fewer pores after being sintered and polished, and the crystallization effect of the crystal nucleus agent dry grains is not influenced. 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 fixing agent can be 1.01-1.02, and 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%. 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 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: 10.5-13.0%, BaO: 0-2.0%, SrO: 1.5-3.0%, loss on ignition: 0.5 to 1.0 percent.
The crystal flower dry grain glaze has high initial melting point, small high temperature viscosity, wide sintering range, and alkali metal flux K in the formula2O 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 dried bean curdCaO, BaO, SrO and ZnO are introduced into the glaze particles, so that the transparency of the dried crystal flower particles is good, the transparency of the fired glaze surface is good after polishing, the transparency is good, the layering sense and the stereoscopic sense of the ceramic ink patterns can be effectively shown, and the beautiful crystal flower effect is separated out from the local position of the glaze surface. Moreover, white crystal flowers with unique artistic effect are separated out at the positions where the crystal nucleus agent dry grains are applied. The ceramic tile adopting the crystal flower dry grain glaze embodies the details of the ink pattern texture and the white crystal flower effect fully, the polished ceramic tile gives people a bright visual impact feeling, and the grade of the architectural ceramic glaze decoration effect is effectively improved.
And then drying, sintering, polishing and edging, and packaging in grades. The maximum firing temperature can be 1190-1220 ℃, and the firing period can be 100-150 minutes.
In one embodiment, a glue pattern is printed by a digital glue drying granulator, a layer of crystal nucleus dry granules are distributed on the glue drying granulator, the crystal nucleus dry granules which are not stuck by glue are sucked away by a recovery system of the digital glue drying granulator under negative pressure for recycling, a layer of crystal flower dry granules glaze is distributed on a common drying granulator, a glue fixing agent is sprayed on the crystal nucleus dry granules glaze for fixing, and the crystal nucleus dry granules glaze is dried and sintered to obtain beautiful crystal flowers separated from the fixed positions of the ceramic tile glaze.
The fixed-point positioning of the crystal nucleus agent dry particles in the crystal flower dry particle glaze is realized through a digital glue dry particle machine, so that beautiful large crystal flowers are presented at the fixed positions of the fired glaze surface. The ceramic tile adopting the crystal nucleus agent dry particles embodies the white crystal pattern effect of the glaze fully, the polished ceramic tile gives a bright visual impact feeling to people, and the grade of the architectural ceramic glaze decoration effect is effectively improved.
In one embodiment, after a layer of inkjet coloring glaze is sprayed on a dried green body by a high-pressure water jet machine, an ink pattern is printed by a digital inkjet machine, a glue pattern is printed by a digital glue dry granulation machine, crystal nucleus agent dry granules are distributed by a distribution machine, redundant crystal nucleus agent dry granules which are not stuck by glue are recovered by a negative pressure system for recycling, a layer of crystal flower dry granule glaze is distributed by a common dry granulation machine, a glue fixing agent is sprayed by the high-pressure water jet machine, and the crystal flower dry granules are dried by a drying kiln and then are sintered. After the ceramic tile is fired, positioned white crystal flowers are separated out at the positions where the crystal nucleus agent is distributed, and no crystal flowers are separated out at the positions where the crystal nucleus agent is not distributed.
The glazed tile obtained by the method has a double-layer pattern effect, high-definition ink pattern layers are arranged under the glaze, and white crystal pattern layers with unique artistic effects are arranged on the glaze. The fixed-point positioning of the white crystal flower is realized through a digital glue grain dryer, and the glaze surface is separated out at the position distributed with the crystal nucleus agent after sintering, so that the positioning crystal flower effect with unique artistic impression is realized.
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 ink-jet coloring glaze on the dried green brick in a glaze spraying manner, wherein the ink-jet coloring glaze comprises the following mineral compositions: potassium feldspar: 43%, albite: 15%, kaolin: 27%, calcined alumina: 5%, zirconium silicate: 8 percent. The chemical composition of the ink-jet coloring glaze is as follows: SiO 22：57.68％、Al2O3：23.57％、Fe2O3：0.4％、TiO2：0.07％、CaO：0.34％、MgO：0.22％、K2O：5.21％、Na2O：2.39％、ZrO2: 6.46%, loss on ignition: 3.38 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: dry granule machine with digital gluePrinting a glue pattern, distributing a layer of crystal nucleus agent dry particles by using a digital glue dry particle machine, and simultaneously pumping out the crystal nucleus agent dry particles which are not stuck by the glue by using the negative pressure of a recovery system 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. The distribution amount of the crystal nucleus agent dry particles is 400g/m2。
Step six: distributing a layer of crystal flower dry grain glaze by using a common dry grain machine, wherein the mineral composition of the crystal flower dry grain glaze is as follows: 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 seven: spraying the glue fixing agent by a high-pressure water jet machine to form a glue fixing agentAnd fixing the dry cloth particles. The specific gravity of the fixing agent is 1.01, and the application amount is 280g/m2。
Step eight: 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 1213 ℃, and the firing period is 110 min.
Step nine: 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, showing that the surface of the ceramic tile has not only a bright stone texture pattern but also a number of white fixed-point positioned cubic crystal effect pattern layers.
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/T13891-2008 (determination of specular glossiness of building decorative materials).
The ceramic tile glaze obtained in example 1 has abrasion resistance of 1500 revolutions, 3 grades, contamination resistance of 3 grades and glossiness of 92-96 degrees after polishing.
Example 2
The difference from example 1 is that: the crystal nucleus agent comprises the following raw materials: : potassium feldspar: 20%, albite: 10% and quartz: 12%, alumina: 1% and calcite: 16%, zinc oxide: 10%, fluorite: 2%, boric acid: 2%, calcium phosphate: 1.5%, rutile: 16% and zircon powder: 8%, tungsten oxide: 1.5 percent. The chemical composition of the crystal nucleating agent is as follows: SiO 22：38.75％、Al2O3：6.40％、Fe2O3：0.10％、TiO2：16.92％、CaO：11.33％、MgO：0.28％、K2O：1.95％、Na2O：1.74％、ZnO：10.58％、F：0.82％、ZrO2：5.56％、P2O5：0.72％、B2O3：1.18％、WO3: 1.59%, loss on ignition: 1.76 percent.
FIG. 4 is a photograph of the surface of the ceramic tile produced in example 2, showing that the surface of the ceramic tile has not only a bright stone texture pattern but also a number of white fixed-point positioned cubic crystal effect pattern layers.
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/T13891-2008 (determination of specular glossiness of building decorative materials).
The ceramic tile glaze obtained in example 2 has an abrasion resistance of 1500 rpm, a level of 4, a stain resistance of 3, and a gloss of 90-95 degrees after polishing.
Example 3
The difference from example 1 is that: the crystal nucleus agent comprises the following raw materials: potassium feldspar: 25% and albite: 5% and quartz: 14%, alumina: 1.5%, calcite: 14%, zinc oxide: 8% and fluorite: 3%, boric acid 3%, calcium phosphate 1%, rutile: 16.5%, zircon powder 7%, tungsten oxide: 2 percent. The chemical composition of the crystal nucleating agent is as follows: SiO 22：40.15％、Al2O3：6.90％、Fe2O3：0.10％、TiO2：17.39％、CaO：10.38％、MgO：0.25％、K2O：2.39％、Na2O：1.42％、ZnO：8.44％、F：1.22％、ZrO2：4.80％、P2O5：0.52％、B2O3：1.77％、WO3: 2.11%, loss on ignition: 1.68 percent.
FIG. 5 is a photograph of the surface of the ceramic tile produced in example 3, showing that the surface of the ceramic tile has not only a bright stone texture pattern but also a number of white fixed-point positioned cubic crystal effect pattern layers.
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/T13891-2008 (determination of specular glossiness of building decorative materials).
The ceramic tile glaze obtained in example 3 has an abrasion resistance of 1500 rpm, a level of 3, a stain resistance of 4, and a gloss of 93-97 degrees after polishing.
Comparative example 1
The difference from example 1 is that: the mineral composition of the crystal nucleus agent is as follows: potassium feldspar: 27%, albite: 5%, quartz: 14%, alumina: 1.5%, calcite 14%, zinc oxide 8%, boric acid: 5%, rutile: 16.5%, zircon powder: 7%, tungsten oxide: 2 percent. The chemical composition of the crystal nucleating agent is as follows: SiO 22：41.81％、Al2O3：7.24％、Fe2O3：0.078％、TiO2：17.68％、CaO：8.62％、MgO：0.18％、K2O：3.07％、Na2O：1.16％、ZnO：8.58％，ZrO2：4.85％，B2O3：2.98％，WO5: 2.14%, loss on ignition: 1.63 percent.
Fig. 6 is a photograph of the tile surface of the ceramic tile manufactured in comparative example 1, and it can be seen that although the tile surface has a bright stone texture pattern, there are only some fine white pattern effects at the fixed-point positioning position, and there is no macroscopic white large crystal flower.
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/T13891-2008 (determination of specular glossiness of building decorative materials).
The ceramic tile glaze obtained in the comparative example 1 has the abrasion resistance of 1500 turns, the level 3, the pollution resistance of 4, and the glossiness of the polished glaze of 94-98 degrees.

Claims (7)

1. A crystal nucleus agent, characterized in that 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.
2. A crystal nucleus agent according to claim 1, characterized in that the crystal nucleus agent is obtained by the following method: the raw materials are mixed according to a ratio and melted into glass liquid at the temperature of 1500-1550 ℃, and the glass liquid is processed into 60-120 mesh dry particles after water quenching.
3. A crystal nucleus agent according to claim 1 or 2, characterized in that the chemical composition of the crystal nucleus 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.
4. A ceramic tile produced using the crystal nucleating agent 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 the crystal nucleus agent on the blank body printed with the pattern;
applying crystal flower dry grain glaze on the blank body coated with the crystal nucleus agent;
and sintering the blank body coated with the crystal flower dry grain glaze, and polishing by adopting a full polishing process.
6. The method according to claim 5, wherein the blank is subjected to glazing and then ink-jet printing of a pattern; preferably, the glaze is an inkjet coloring glaze; more preferably, the raw materials of the inkjet coloring glaze comprise: according to mass percent, potassium feldspar: 33-45%, albite: 15-25% of kaolin: 22-27% of calcined alumina: 5-9%, zirconium silicate: 8-10%; preferably, the chemistry of the inkjet-pigmented glazeThe composition comprises: by mass percent, SiO2：55.0～60.0%、Al2O3：23.5～25.5%、Fe2O3：0～0.5%、TiO2：0～0.1%、CaO：0～0.5%、MgO：0～0.3%、K2O：4.0～5.5%、Na2O：2.0～3.5%、ZrO2: 8.0-12.0%, loss on ignition: 3.0 to 4.5 percent.
7. The preparation method according to any one of claims 5 to 6, wherein 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%; 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.
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