CN116040945A - Ceramic tile base glaze, ceramic tile and preparation method thereof - Google Patents
Ceramic tile base glaze, ceramic tile and preparation method thereof Download PDFInfo
- Publication number
- CN116040945A CN116040945A CN202310052338.0A CN202310052338A CN116040945A CN 116040945 A CN116040945 A CN 116040945A CN 202310052338 A CN202310052338 A CN 202310052338A CN 116040945 A CN116040945 A CN 116040945A
- Authority
- CN
- China
- Prior art keywords
- parts
- ceramic tile
- primer
- glaze
- frit
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 186
- 238000002360 preparation method Methods 0.000 title abstract description 13
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052656 albite Inorganic materials 0.000 claims abstract description 33
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 239000000454 talc Substances 0.000 claims abstract description 28
- 235000012222 talc Nutrition 0.000 claims abstract description 28
- 229910052623 talc Inorganic materials 0.000 claims abstract description 28
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 22
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 22
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052599 brucite Inorganic materials 0.000 claims abstract description 18
- 230000001681 protective effect Effects 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- 239000010453 quartz Substances 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 24
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 19
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 15
- 238000010304 firing Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 238000005034 decoration Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 63
- 235000010215 titanium dioxide Nutrition 0.000 abstract description 49
- 239000012071 phase Substances 0.000 abstract description 29
- 239000011777 magnesium Substances 0.000 abstract description 24
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052749 magnesium Inorganic materials 0.000 abstract description 18
- 238000003746 solid phase reaction Methods 0.000 abstract description 18
- 238000002844 melting Methods 0.000 abstract description 15
- 230000008018 melting Effects 0.000 abstract description 15
- 238000005245 sintering Methods 0.000 abstract description 10
- 239000002253 acid Substances 0.000 abstract description 9
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000002425 crystallisation Methods 0.000 abstract description 5
- 230000008025 crystallization Effects 0.000 abstract description 5
- 238000005507 spraying Methods 0.000 description 17
- 239000011521 glass Substances 0.000 description 13
- 239000000839 emulsion Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000004408 titanium dioxide Substances 0.000 description 10
- 229910010413 TiO 2 Inorganic materials 0.000 description 9
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 9
- 239000001768 carboxy methyl cellulose Substances 0.000 description 9
- 238000005265 energy consumption Methods 0.000 description 9
- 230000005484 gravity Effects 0.000 description 9
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 9
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 210000003298 dental enamel Anatomy 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 238000004383 yellowing Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 235000019832 sodium triphosphate Nutrition 0.000 description 5
- 239000010433 feldspar Substances 0.000 description 4
- 238000007641 inkjet printing Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- 229910052596 spinel Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000011449 brick Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- BLJNPOIVYYWHMA-UHFFFAOYSA-N alumane;cobalt Chemical compound [AlH3].[Co] BLJNPOIVYYWHMA-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- CRHLEZORXKQUEI-UHFFFAOYSA-N dialuminum;cobalt(2+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Co+2].[Co+2] CRHLEZORXKQUEI-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052572 stoneware Inorganic materials 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B11/00—Apparatus or processes for treating or working the shaped or preshaped articles
- B28B11/001—Applying decorations on shaped articles, e.g. by painting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B11/00—Apparatus or processes for treating or working the shaped or preshaped articles
- B28B11/04—Apparatus or processes for treating or working the shaped or preshaped articles for coating or applying engobing layers
- B28B11/044—Apparatus or processes for treating or working the shaped or preshaped articles for coating or applying engobing layers with glaze or engobe or enamel or varnish
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B11/00—Apparatus or processes for treating or working the shaped or preshaped articles
- B28B11/04—Apparatus or processes for treating or working the shaped or preshaped articles for coating or applying engobing layers
- B28B11/048—Apparatus or processes for treating or working the shaped or preshaped articles for coating or applying engobing layers by spraying or projecting
-
- 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
-
- 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
- C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
-
- 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
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- 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
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
-
- 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
-
- 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
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
Abstract
The invention discloses a ceramic tile primer, a ceramic tile and a preparation method thereof, wherein the ceramic tile primer comprises the following raw materials in parts by mass: 6-12 parts of kaolin, 0-40 parts of potassium feldspar and/or albite, 5-15 parts of meta-titanic acid, 10-32 parts of brucite, 7-30 parts of talcum and 15-31 parts of low-temperature frit. The ceramic tile base glaze provided by the invention does not need to use zirconium silicate with high price or titanium white frit, and metatitanic acid and brucite are introduced into the ceramic tile base glaze formula, and a magnesium titanate opacifying phase is generated through solid phase reaction, the glaze gloss is less than 10 ℃, and the whiteness is between 60 and 70 ℃, so that the color of a ceramic blank is covered. The ceramic tile primer provided by the invention realizes the function of serving as the primer based on solid phase reaction, crystallization is not needed, sintering to melting is not needed, the use of silicon-aluminum components in the primer is more relaxed than that of the primer containing titanium white frit, and the ceramic tile primer can be sintered at a high temperature of 1150-1250 ℃.
Description
Technical Field
The invention relates to the technical field of building ceramic bricks, in particular to a ceramic brick base glaze, a ceramic brick and a preparation method thereof.
Background
In the building ceramic industry, the base glaze has higher whiteness and extremely strong covering effect. The base glaze uses substances with higher refractive index as an emulsion phase to reflect visible light and cover the blank color. Common opacifiers for ceramic tile underglaze include cerium oxide, tin oxide, zirconium silicate, titanium dioxide and the like. Wherein, cerium oxide and tin oxide are high in price and rarely used; the zirconium silicate has high refractive index (1.93-2.01), wide adaptability to the formula of the primer, capability of improving the physicochemical properties of the primer, and the like, and the zirconium silicate has radioactivity due to trace hafnium element, but does not prevent the wide application of the zirconium silicate in ceramic tile production. However, in recent years, the price of zirconium silicate has increased, and there has been an urgent need for a substitute which is strong in opacifying ability and low in price to replace zirconium silicate. Titanium dioxide is also an oxide with high refractive index, the refractive index is as high as 2.55-2.76, the titanium dioxide has extremely strong reflection effect on light, is the whitest material in the world, can replace zirconium silicate to be used as the main component of waterproof ground glaze to be applied to building ceramic tile products, and is usually introduced in the form of conventional titanium white frit, in particular titanium dioxide is mostly mixed with SiO 2 Raw materials such as CaO and the like are sintered into low-temperature titanium white frit which is used in the ground glaze of glazed tiles (commonly called ceramic tiles) and is sintered at 1020-1050 ℃, and the opacified phase is sphene. However, the titanium white frit has the following technical bottlenecks in the use process:
firstly, the melting temperature of the titanium white frit is low, and the titanium white frit is more suitable for being used under a ceramic tile firing system of 1020-1050 ℃. When the titanium white frit which can be melted at low temperature is used for firing at about 1200 ℃, the glaze surface can be sealed due to too low melting temperature of the titanium white frit, so that gas of a ceramic body in an oxidation exhaust stage is not easy to discharge, the glaze surface is easy to have defects of pinhole bubbles and the like, and meanwhile, the glaze surface has too high glossiness due to low melting temperature and does not meet the performance requirements of ceramic tile ground coat, therefore, the prior titanium white frit has limited use temperature and cannot be used in ceramic or stoneware building ceramic tile products fired at 1150-1250 ℃.
Next, in order to enhance melting of the primerTemperature is increased to increase Al in the formula 2 O 3 The ratio of the titanium white frit is a common means, however, the crystallization of the sphene by adopting the primer of the titanium white frit is performed only when the high-temperature viscosity is not large after the glaze is melted due to supersaturation of crystalline phase components and supercooling of a temperature system. Al (Al) 2 O 3 Although the addition of the (B) can raise the melting temperature of the primer, the capability of raising the high-temperature viscosity of the primer is extremely strong, so that Al in the primer 2 O 3 The titanium white frit has a limited applicable primer formulation, and can not be used in the primer with high alumina content.
Finally, on one hand, the titanium white frit is required to be fired at a high temperature, and both frit melting and frit crushing are energy-consuming processes, so that the cost is high; on the other hand, since titanium dioxide content in the titanium white frit is low, a large amount of titanium white frit is required to ensure whiteness and hiding effect of the primer, and in general, tiO in the primer 2 The content is controlled to be 5-8wt% so as to meet the whiteness requirement of ceramic tile products. However, in the existing titanium white frit, tiO 2 The content is usually 7.12 to 13.85 weight percent, and the base coat is TiO 2 The content of the titanium white frit in the base glaze is as 6wt percent, and the use level of the titanium white frit in the base glaze is required to reach 42-83 wt percent. Namely, a large amount of titanium white fused cakes which are melted at high temperature are required to be used in the formula, so that the manufacturing cost, the energy consumption and the carbon emission are further increased. Therefore, the use of the titanium white frit causes great consumption of social resources, great energy consumption and high cost.
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
Based on the defects of the prior art, the invention aims to provide a ceramic tile primer, a ceramic tile and a preparation method thereof, and aims to solve the problems that titanium white frit used in the prior ceramic tile primer is high in cost, limited in applicable primer formula and limited in use temperature.
The technical scheme of the invention is as follows:
the invention provides a ceramic tile primer, which comprises the following raw materials in parts by mass:
6-12 parts of kaolin, 0-40 parts of potassium feldspar and/or albite, 5-15 parts of meta-titanic acid, 10-32 parts of brucite, 7-30 parts of talcum and 15-31 parts of low-temperature frit.
Optionally, the raw materials of the ceramic tile base coat comprise the following components in parts by mass:
6-12 parts of kaolin, 7-40 parts of potassium feldspar and/or albite, 5-15 parts of meta-titanic acid, 10-32 parts of brucite, 7-30 parts of talcum and 15-31 parts of low-temperature frit.
Optionally, the chemical components of the low-temperature frit comprise, in parts by weight:
SiO 2 55-65 parts of Al 2 O 3 6 to 12 parts of Fe 2 O 3 0 to 0.3 part, 8 to 12 parts of CaO, 0.5 to 3 parts of MgO and K 2 O2-6 parts, na 2 0.5 to 3 parts of O, 5 to 14 parts of ZnO and B 2 O 3 0.5 to 3 parts of BaO and 0 to 0.5 part of BaO.
Optionally, the chemical components of the low-temperature frit comprise, in parts by weight:
SiO 2 55-65 parts of Al 2 O 3 6 to 12 parts of Fe 2 O 3 0.1 to 0.3 part, 8 to 12 parts of CaO, 0.5 to 3 parts of MgO and K 2 O2-6 parts, na 2 0.5 to 3 parts of O, 10 to 14 parts of ZnO and B 2 O 3 1 to 3 parts of BaO and 0.1 to 0.5 part of BaO.
Optionally, the raw materials of the ceramic tile base coat further comprise, by mass: quartz 0-15 parts.
According to a second aspect of the invention, a ceramic tile is provided, which comprises a ceramic body, a primer layer, an inkjet decorative layer and a surface glaze layer which are sequentially laminated, and is characterized in that the primer layer is prepared from the ceramic tile primer disclosed by the invention.
Optionally, the ceramic tile further comprises:
the protective glaze layer is arranged between the ground glaze layer and the inkjet decorative layer;
the protective glaze layer is prepared from the following raw materials in parts by mass:
8-12 parts of kaolin, 10-25 parts of potassium feldspar, 10-25 parts of albite, 8-20 parts of zirconium silicate, 0-10 parts of alumina, 0-10 parts of calcined talcum, 0-15 parts of quartz and 15-30 parts of frit.
Optionally, the chemical components of the frit include, in parts by weight:
SiO 2 55-65 parts of Al 2 O 3 6 to 12 parts of ZrO 2 4 to 8 parts of Fe 2 O 3 0 to 0.3 part, 5 to 10 parts of CaO, 4 to 8 parts of MgO and K 2 O4-8 parts, na 2 0.5 to 3 portions of O.
In a third aspect of the present invention, there is provided a method for producing the ceramic tile of the present invention as described above, comprising the steps of:
providing a ceramic body;
applying the ceramic tile base coat of any one of claims 1-5 to the ceramic body, then performing inkjet decoration and applying an overglaze;
firing is carried out at 1150-1250 ℃ to obtain the ceramic tile which comprises a ceramic body, a ground coat layer, an inkjet decorative layer and a surface coat layer which are sequentially laminated.
Optionally, after the ceramic tile base glaze is applied and before the inkjet decoration, the method further comprises the step of applying a protective glaze, wherein the raw materials of the protective glaze comprise the following components in parts by mass:
8-12 parts of kaolin, 10-25 parts of potassium feldspar, 10-25 parts of albite, 8-20 parts of zirconium silicate, 0-10 parts of alumina, 0-10 parts of calcined talcum, 0-15 parts of quartz and 15-30 parts of frit.
The beneficial effects are that: the ceramic tile base glaze provided by the invention has high whiteness, and is a matte glaze with strong blank color covering capability. The ceramic tile base glaze does not need to use zirconium silicate with high price or titanium white frit, and meta-titanic acid and brucite are introduced into the ceramic tile base glaze formula to generate magnesium titanate emulsion through solid phase reaction, the glaze gloss is less than 10 ℃, and the whiteness is between 60 and 70, so that the color of a ceramic blank is covered. The ceramic tile primer provided by the invention is based on a solid phase reaction to realize the function of the primer, namely, the opacified magnesium titanate crystalline phase is synthesized through the solid phase reaction, crystallization is not needed, sintering to melting is not needed (the primer sintering is needed), and further, the requirement that the high-temperature viscosity of the primer after melting is lower is not met, and the primer can contain higher content of aluminum oxide, so that the use of silicon-aluminum components in the primer is more relaxed than that of the primer containing titanium white frit, and the ceramic tile primer can be sintered at the high temperature of 1150-1250 ℃ by adopting the ceramic tile primer disclosed by the invention, so that the problems that the cost of using titanium white frit in the ceramic tile primer is high, the energy consumption is high, the use temperature is limited (the ceramic tile primer cannot be sintered at the high temperature), and the applicable primer formula is limited (the ceramic tile primer cannot be used in the primer with high aluminum oxide content) are avoided.
Detailed Description
The invention provides a ceramic tile base glaze, a ceramic tile and a preparation method thereof, which are used for making the purposes, the technical scheme and the effects of the invention clearer and more definite, and the invention is further described in detail below. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The embodiment of the invention provides a ceramic tile primer, wherein the raw materials of the ceramic tile primer comprise the following components in parts by mass:
6-12 parts of kaolin, 0-40 parts of potassium feldspar and/or albite, 5-15 parts of meta-titanic acid, 10-32 parts of brucite, 7-30 parts of talcum and 15-31 parts of low-temperature frit.
The ceramic tile base glaze provided by the embodiment of the invention has high whiteness, and is a matte glaze with strong blank color covering capability. The ceramic tile base glaze does not need to use zirconium silicate with high price or titanium white frit, and meta-titanic acid and brucite are introduced into the ceramic tile base glaze formula to generate magnesium titanate emulsion through solid phase reaction, the glaze gloss is less than 10 ℃, and the whiteness is between 60 and 70, so that the color of a ceramic blank is covered. The ceramic tile primer provided by the embodiment of the invention realizes the function of the primer based on solid phase reaction, namely the opacified magnesium titanate crystalline phase is synthesized through the solid phase reaction, crystallization is not needed, sintering to melting (the primer sintering is needed), and further, the requirement that the high-temperature viscosity of the primer after melting is lower (the conventional primer adopting titanium white frit is needed when the high-temperature viscosity of the primer after melting is not great) is not met, the primer can contain higher content of aluminum oxide, namely the use of silicon-aluminum components in the primer is more relaxed than that of the primer containing the titanium white frit, and the ceramic tile primer adopting the embodiment of the invention can be sintered at the high temperature of 1150-1250 ℃ (namely the ceramic tile primer can be used in ceramic tiles sintered at the high temperature of 1150-1250 ℃). The ceramic tile primer provided by the invention does not use titanium white frit, so that the problems of high cost, high energy consumption, limited use temperature (not high-temperature firing) and limited applicable primer formula (not used in the primer with high alumina content) caused by using the titanium white frit in the ceramic tile primer are avoided.
In this example, the magnesium titanate emulsion phase was formed by Mg (OH) 2 With TiO 2 Is produced by solid phase reaction of (a) and has the following specific reaction formula:
in the reaction, mg (OH) 2 Brucite (Mg (OH) 2 ) Is introduced in the form of (c). Brucite with relative density of 2.3-2.6, hardness of 2.5, easy ball milling processing, theoretical chemical composition of MgO 69.12wt% and H 2 O30.88 wt%, and decomposing into MgO and H at about 450 DEG C 2 O。TiO 2 Then the catalyst is introduced in the form of metatitanic acid which is an amphoteric compound with a molecular formula of TiO (OH) 2 The titanium dioxide content is about 91%, and the meta-titanic acid is an intermediate product of titanium dioxide produced by a sulfuric acid method, so that the meta-titanic acid is prepared by a chemical method, is amorphous, is extremely easy to grind to a micron level, can be dehydrated at a high temperature, has high reaction activity, ensures that the solid phase reaction is quicker and more complete, and is very suitable for being used for synthesizing a magnesium titanate emulsion phase by a solid phase reaction methodRaw materials. In the present invention, tiO 2 The meta-titanic acid is introduced in a form of amorphous and easy to ball mill, and can be dehydrated at high temperature; mg (OH) 2 Introducing the mixture into brucite form, and dehydrating the mixture at about 450 ℃; the selection of the two raw materials accords with the principle of improving the solid phase reaction efficiency and speed of the inorganic material.
The main process steps for producing titanium dioxide by the sulfuric acid method are as follows:
①TiO 2 acidolysis of the raw materials with sulfuric acid;
(2) settling, and separating soluble titanyl sulfate from solid impurities;
(3) hydrolyzing titanyl sulfate to form a water insoluble hydrolysate, namely meta-titanic acid;
(4) calcining to remove water and generate dry pure TiO 2 And controlling firing temperature and other systems to prepare the titanium dioxide with different crystal forms such as rutile or anatase.
Therefore, the process steps show that the metatitanic acid is an intermediate product for producing titanium dioxide by a sulfuric acid method, so that the use of the metatitanic acid has lower cost and has great benefit for society, namely, the carbon emission is reduced.
In this example, when Mg (OH) 2 With TiO 2 When the mass ratio of (2) is 1.5:1, the generated crystal phase is mainly white meta-titanic acid (Mg) 2 TiO 4 ) While when Mg (OH) 2 Is less in content of Mg (OH) 2 With TiO 2 The mass ratio of (2) is less than 1.5:1, rutile is easy to generate, the ground coat is yellow, and therefore, mg (OH) should be controlled 2 With TiO 2 The mass of (2) is 1.5:1 or more. TiO in meta-titanic acid 2 The content is about 91%, so that the dosage of the metatitanic acid in the ceramic tile base glaze can be converted.
In this example, kaolin is plastic material, and provides suspension property and silicon-aluminum component for glaze slurry, and potassium feldspar and albite can form glass phase at high temperature to solidify glaze layer. The magnesium titanate can be symbiotic with talcum, and talcum can improve the firing temperature of the ceramic tile base glaze, so that talcum is introduced, and the ratio between talcum and low-temperature frit is adjusted to the ratio described in the embodiment, so that the ceramic tile base glaze can be fired at the high temperature of 1150-1250 ℃ (namely, the base glaze can be applied to ceramic tile products with the firing temperature of 1150-1250 ℃). One purpose of adding low temperature frits is to work in concert with talc so that the ceramic tile primer can be used in ceramic tiles employing a high temperature firing regime; another purpose of adding the low temperature frit is to generate a high temperature liquid phase earlier than potassium feldspar and albite to promote the solid phase reaction of meta-titanic acid with magnesium hydroxide to proceed well and as soon as possible.
In the embodiment, the ceramic tile base glaze comprises 0-40 parts of potassium feldspar and/or albite, namely the ceramic tile base glaze comprises 0-40 parts of potassium feldspar, or the ceramic tile base glaze comprises 0-40 parts of albite, or the ceramic tile base glaze comprises 0-40 parts of potassium feldspar and albite. When the ceramic tile base glaze comprises 0-40 parts of potassium feldspar and albite, the specific parts by weight of the potassium feldspar and albite can be set according to actual needs, for example 10 parts of potassium feldspar and 10 parts of albite; 15 parts of potassium feldspar and 12 parts of albite; 16 parts of potassium feldspar, 18 parts of albite and the like. In addition, the expansion coefficient of the ceramic tile base glaze can be finely adjusted by regulating and controlling the proportion of potassium and sodium in the potassium feldspar and the sodium feldspar.
In one embodiment, the raw materials of the ceramic tile base glaze comprise the following components in parts by mass:
6-12 parts of kaolin, 7-40 parts of potassium feldspar and/or albite, 5-15 parts of meta-titanic acid, 10-32 parts of brucite, 7-30 parts of talcum and 15-31 parts of low-temperature frit.
In this embodiment, the proportion of potassium feldspar and/or sodium feldspar is increased, so that more glass phase is generated, the glass phase fully wraps the magnesium titanate emulsion phase, and the magnesium titanate emulsion phase is prevented from reacting with other substances (such as spinel component in ink-jet ink, etc.), so that the ceramic tile primer can be better applied to ceramic tiles.
In one embodiment, the low temperature frit comprises the following chemical components in parts by weight:
SiO 2 55-65 parts of Al 2 O 3 6 to 12 parts of Fe 2 O 3 0 to 0.3 part, 8 to 12 parts of CaO, 0.5 to 3 parts of MgO and K 2 O2-6 parts, na 2 O 0.5～3 parts of ZnO 5-14 parts of B 2 O 3 0.5 to 3 parts of BaO and 0 to 0.5 part of BaO.
In the embodiment, the low-temperature frit of the chemical component generates a high-temperature liquid phase earlier than the potassium feldspar and the albite, which is more beneficial to promoting the solid-phase reaction of the meta-titanic acid and the magnesium hydroxide to be carried out as soon as possible. Meanwhile, the low-temperature frit of the chemical components and talcum work together, so that the ceramic tile base glaze can be suitable for ceramic tiles fired at the high temperature of 1150-1250 ℃.
In some specific embodiments, the low temperature frit comprises the following chemical components in parts by weight:
SiO 2 55-65 parts of Al 2 O 3 6 to 12 parts of Fe 2 O 3 0.1 to 0.3 part, 8 to 12 parts of CaO, 0.5 to 3 parts of MgO and K 2 O2-6 parts, na 2 0.5 to 3 parts of O, 10 to 14 parts of ZnO and B 2 O 3 1 to 3 parts of BaO and 0.1 to 0.5 part of BaO.
Further, in order to increase the expansion coefficient of the ceramic tile primer, in one embodiment, the raw materials of the ceramic tile primer further include, in parts by mass: quartz 0-15 parts, wherein the quartz is not 0 part.
As the specifications of ceramic tile products are larger and larger, the influence of the expansion coefficient of the primer on the tile type is larger and larger, so that the expansion coefficient becomes one of key factors of success and failure of the primer formula. In general, two means are often adopted for adjusting the expansion coefficient of the ceramic tile base glaze, namely, a high-expansion frit is used, the expansion coefficient of the frit is large, but in order to raise the melting temperature of the base glaze, the aluminum content of the frit is also high, and the TiO in the base glaze is easy to cause 2 The ground coat is yellow due to precipitation; secondly, quartz is used, and if the quartz is melted into a glass phase in the ground glaze, the quartz becomes a high-silicon glass phase, and the expansion coefficient is reduced; if the silica is not melted into the silica, the expansion coefficient is large. According to the method, quartz with different proportions can be added in the production process to adjust the expansion coefficient of the base coat. If the titanium white frit is used as the primer, the titanium white frit is large in dosage, more glass phase is added, more quartz is fused into the glass phase, the expansion coefficient of the primer is easy to be reduced, and the primer is difficult to be enlarged. Namely when the titanium white frit is used as the prior ceramic tile base glazeThe expansion coefficient is inconvenient to adjust. In the present embodiment, the titanium white frit is not used, and the glass phase is relatively small, and the quartz capable of adjusting the expansion coefficient of the primer is not easy to melt into the glass phase, so that the expansion coefficient of the ceramic tile primer can be effectively improved by adding the quartz. According to actual needs, quartz is added when the expansion coefficient of the ceramic tile base glaze needs to be further improved.
The embodiment of the invention also provides a ceramic tile, which comprises a ceramic body, a ground glaze layer, an inkjet decorative layer and a surface glaze layer which are sequentially laminated, wherein the ground glaze layer is prepared from the ground glaze of the ceramic tile. In the embodiment, zirconium silicate with higher cost is not needed to be used as the ceramic tile base glaze, titanium white frit with high energy consumption is also not needed to be used, the cost is low, the energy consumption is low, social resources are saved, the energy consumption and carbon emission of ceramic production are reduced, and sustainable development can be realized.
In the embodiment of the invention, the opacified magnesium titanate crystalline phase is generated by solid phase reaction, and although the low-temperature frit, the potassium-sodium feldspar and the like can generate a glass phase, when the glossiness of the base glaze is required to be below 10 ℃, namely the content of the low-temperature frit and the potassium-sodium feldspar is low, the generated glass phase is insufficient to enable the magnesium titanate opacified phase to be completely wrapped. Further, when ink-jet printing is performed on the ceramic tile base, the colorant in the ink-jet ink reacts easily with the magnesium titanate emulsion which is not encapsulated by the glass phase, resulting in a yellowish pattern. Specifically, taking blue ink as an example, the blue ink uses nano cobalt aluminate spinel as a pigment, when the ceramic tile base glaze provided by the invention cannot be fully wrapped by a glass phase during high-temperature calcination, the magnesium titanate emulsion contacts with the spinel and is sintered, and TiO in the magnesium titanate emulsion phase 2 And Al in nano cobalt aluminum spinel 2 O 3 React to generate Al 2 TiO 5 。Al 2 TiO 5 In the process of cooling, the catalyst is decomposed into TiO 2 And Al 2 O 3 ，TiO 2 The rutile is generated to be yellow when the material is burned at a high temperature of more than 1100 ℃, and the product is yellow. Based on this, in one embodiment of the present invention, the ceramic tile further comprises:
the protective glaze layer is arranged between the ground glaze layer and the inkjet decorative layer;
the protective glaze layer is prepared from the following raw materials in parts by mass:
8-12 parts of kaolin, 10-25 parts of potassium feldspar, 10-25 parts of albite, 8-20 parts of zirconium silicate, 0-10 parts of alumina, 0-10 parts of calcined talcum, 0-15 parts of quartz and 15-30 parts of frit.
In the embodiment, the zirconium white ground enamel of the raw material component is adopted as the protective glaze, the protective glaze plays a role of isolating the ceramic tile ground enamel from the ink-jet ink, the contact of the ceramic tile ground enamel with pigment in the ink-jet ink is avoided, the damage of the magnesium titanate emulsion phase component in the ground enamel is further avoided, the generation of golden red stone is avoided, and the phenomenon of yellowing of the ceramic tile ground enamel is avoided. The ground coat layer prepared from the ceramic tile ground coat is matched with the protective glaze layer, so that the cost and energy consumption of the ceramic tile can be reduced, the firing at high temperature can be realized, the ground coat of the ceramic tile can be prevented from reacting with ink-jet ink, and the yellowing of the layout of the ceramic tile is avoided.
In one embodiment, the protective glaze layer is prepared from the following raw materials in parts by mass:
8-12 parts of kaolin, 10-25 parts of potassium feldspar, 10-25 parts of albite, 8-20 parts of zirconium silicate, 7-10 parts of alumina, 8-10 parts of calcined talcum, 10-15 parts of quartz and 15-30 parts of frit.
In one embodiment, the frit comprises the chemical composition:
SiO 2 55-65 parts of Al 2 O 3 6 to 12 parts of ZrO 2 4 to 8 parts of Fe 2 O 3 0 to 0.3 part, 5 to 10 parts of CaO, 4 to 8 parts of MgO and K 2 O4-8 parts, na 2 0.5 to 3 portions of O.
The embodiment of the invention also provides a preparation method of the ceramic tile, which is characterized by comprising the following steps:
s1, providing a ceramic blank;
s2, applying the ceramic tile base glaze according to the embodiment of the invention on the ceramic blank, and then performing inkjet decoration and applying overglaze;
and S3, sintering at 1150-1250 ℃ to obtain the ceramic tile which comprises a ceramic body, a ground glaze layer, an inkjet decorative layer and a surface glaze layer which are sequentially laminated.
The invention does not limit the specific components of the ceramic blank in the step S1, and the existing ceramic blank is adopted.
In step S2, the ceramic tile base enamel according to the embodiment of the present invention may be mixed with water and additives (e.g., sodium carboxymethylcellulose and sodium tripolyphosphate) to form a base enamel slurry, and then applied (e.g., sprayed by a high-pressure spraying cabinet) onto the ceramic body.
The ink and the overglaze used for the inkjet decoration are not particularly limited, and the ink and the overglaze in the prior art can be used.
In some embodiments, after applying the ceramic tile primer, and before performing inkjet decoration, the method further comprises the step of applying a protective glaze, wherein the raw materials of the protective glaze comprise the following components in parts by mass:
8-12 parts of kaolin, 10-25 parts of potassium feldspar, 10-25 parts of albite, 8-20 parts of zirconium silicate, 0-10 parts of alumina, 0-10 parts of calcined talcum, 0-15 parts of quartz and 15-30 parts of frit.
Preparing the protective glaze slurry with the specific gravity of 1.4 from the protective glaze of the raw material components and water, and spraying by adopting a high-pressure glaze spraying cabinet or printing on the ceramic tile base glaze by adopting a rubber roll printer. The glaze including the ceramic tile base glaze and the protective glaze is used in the form of glaze slip, and the use mode of the glaze and the preparation method of the glaze slip in the prior art can be referred.
In one embodiment, the frit comprises the following chemical components in parts by weight:
SiO 2 55-65 parts of Al 2 O 3 6 to 12 parts of ZrO 2 4 to 8 parts of Fe 2 O 3 0 to 0.3 part, 5 to 10 parts of CaO, 4 to 8 parts of MgO and K 2 O4-8 parts, na 2 0.5 to 3 portions of O.
The invention is further illustrated by the following specific examples.
Example 1
The embodiment provides a ceramic tile primer, which comprises the following raw materials in parts by mass:
8 parts of kaolin, 5 parts of potassium feldspar, 6 parts of albite, 10 parts of metatitanic acid, 20 parts of brucite, 23 parts of talcum and 28 parts of low-temperature frit. Wherein, tiO in the meta-titanic acid 2 The content of (2) was 91%.
The low-temperature frit comprises the following chemical components in parts by mass:
SiO 2 59.22 parts, al 2 O 3 9.19 parts of Fe 2 O 3 0.12 part, caO 9.82 parts, mgO 1.02 parts, K 2 O4.48 parts, na 2 0.85 part of O, 12.88 parts of ZnO and B 2 O 3 1.16 parts of BaO 0.17 parts and loss on ignition 0.54 parts.
Through tests, the whiteness of the ceramic tile base glaze is 63, the green can be effectively covered, and the application requirement of the base glaze is met.
Example 2
The embodiment provides a ceramic tile primer, which comprises the following raw materials in parts by mass:
8 parts of kaolin, 3 parts of potassium feldspar, 4 parts of albite, 15 parts of metatitanic acid, 32 parts of brucite, 7 parts of talcum and 31 parts of low-temperature frit. Wherein, tiO in the meta-titanic acid 2 The content of (2) was 91%.
The low-temperature frit comprises the following chemical components in parts by mass:
SiO 2 59.22 parts, al 2 O 3 9.19 parts of Fe 2 O 3 0.12 part, caO 9.82 parts, mgO 1.02 parts, K 2 O4.48 parts, na 2 0.85 part of O, 12.88 parts of ZnO and B 2 O 3 1.16 parts of BaO 0.17 parts and loss on ignition 0.54 parts.
Through testing, the whiteness of the ceramic tile base glaze is 66, the green can be effectively covered, and the application requirement of the base glaze is met.
Example 3 this example provides a ceramic tile primer, the raw materials of ceramic tile primer include the following components according to the weight portion:
Gao Ling12 parts of soil, 10 parts of potassium feldspar, 20 parts of albite, 6 parts of metatitanic acid, 15 parts of brucite, 25 parts of talcum and 15 parts of low-temperature frit. Wherein, tiO in the meta-titanic acid 2 The content of (2) was 91%.
The low-temperature frit comprises the following chemical components in parts by mass:
SiO 2 59.22 parts, al 2 O 3 9.19 parts of Fe 2 O 3 0.12 part, caO 9.82 parts, mgO 1.02 parts, K 2 O4.48 parts, na 2 0.85 part of O, 12.88 parts of ZnO and B 2 O 3 1.16 parts of BaO 0.17 parts and loss on ignition 0.54 parts.
Through tests, the whiteness of the ceramic tile base glaze is 63, the green can be effectively covered, and the application requirement of the base glaze is met.
Example 4
The ceramic tile base glaze comprises the following raw materials in parts by mass:
8 parts of kaolin, 6 parts of potassium feldspar, 5 parts of albite, 10 parts of metatitanic acid, 20 parts of brucite, 23 parts of talcum, 28 parts of low-temperature frit and 10 parts of quartz. Wherein, tiO in the meta-titanic acid 2 The content of (2) was 91%.
The low-temperature frit comprises the following chemical components in parts by mass:
SiO 2 59.22 parts, al 2 O 3 9.19 parts of Fe 2 O 3 0.12 part, caO 9.82 parts, mgO 1.02 parts, K 2 O4.48 parts, na 2 0.85 part of O, 12.88 parts of ZnO and B 2 O 3 1.16 parts of BaO 0.17 parts and loss on ignition 0.54 parts.
Through testing, the whiteness of the ceramic tile base glaze is 64, the green can be effectively covered, and the application requirement of the base glaze is met.
Example 5
The embodiment provides a preparation method of ceramic tiles, which comprises the following steps:
providing a ceramic body;
mixing the ceramic tile base glaze raw material in the example 1 with 0.15 part of sodium carboxymethylcellulose, 0.25 part of sodium tripolyphosphate and water to form ceramic tile base glaze slip with the specific gravity of 1.7, and then spraying the ceramic tile base glaze slip on a ceramic body by adopting a high-pressure glaze spraying cabinet;
then 11 parts of kaolin, 17 parts of potassium feldspar, 16 parts of albite, 10 parts of zirconium silicate, 7 parts of aluminum oxide, 8 parts of calcined talcum, 10 parts of quartz and 21 parts of frit are mixed with 0.13 part of water and 0.25 part of sodium carboxymethylcellulose to form protective glaze slip with the specific gravity of 1.4, and the protective glaze slip is sprayed by a high-pressure glaze spraying cabinet; wherein the chemical components of the frit comprise:
SiO 2 62.13 parts of Al 2 O 3 11.51 parts of ZrO 2 5.25 parts of Fe 2 O 3 0.12 part, 7.57 parts of CaO, 5.17 parts of MgO and K 2 O5.79 parts, na 2 O1.56 parts and loss on ignition 0.15 parts.
Then, blue ink is printed by ink jet, overglaze is sprayed, and firing is carried out at the temperature of 1200 ℃.
Through the test, no pattern yellowing phenomenon is found.
Example 6
The embodiment provides a preparation method of ceramic tiles, which comprises the following steps:
providing a ceramic body;
mixing the ceramic tile base glaze raw material in the example 2 with 0.25 part of sodium carboxymethylcellulose, 0.35 part of sodium tripolyphosphate and water to form ceramic tile base glaze slip with the specific gravity of 1.7, and then spraying the ceramic tile base glaze slip on a ceramic body by adopting a high-pressure glaze spraying cabinet;
then 11 parts of kaolin, 17 parts of potassium feldspar, 16 parts of albite, 10 parts of zirconium silicate, 7 parts of aluminum oxide, 8 parts of calcined talcum, 10 parts of quartz and 21 parts of frit are mixed with 0.13 part of water and 0.25 part of sodium carboxymethylcellulose to form protective glaze slip with the specific gravity of 1.4, and the protective glaze slip is sprayed by a high-pressure glaze spraying cabinet; wherein the chemical components of the frit comprise:
SiO 2 62.13 parts of Al 2 O 3 11.51 parts of ZrO 2 5.25 parts of Fe 2 O 3 0.12 part, 7.57 parts of CaO, 5.17 parts of MgO and K 2 O5.79 parts, na 2 O1.56 parts and loss on ignition 0.15 parts.
Then, blue ink is printed by ink jet, overglaze is sprayed, and firing is carried out at the temperature of 1250 ℃.
Through the test, no pattern yellowing phenomenon is found.
Example 7
The embodiment provides a preparation method of ceramic tiles, which comprises the following steps:
providing a ceramic body;
mixing the ceramic tile base glaze raw material in the example 3 with 0.15 part of sodium carboxymethylcellulose, 0.20 part of sodium tripolyphosphate and water to form ceramic tile base glaze slip with the specific gravity of 1.7, and then spraying the ceramic tile base glaze slip on a ceramic body by adopting a high-pressure glaze spraying cabinet;
then 11 parts of kaolin, 17 parts of potassium feldspar, 16 parts of albite, 10 parts of zirconium silicate, 7 parts of aluminum oxide, 8 parts of calcined talcum, 10 parts of quartz and 21 parts of frit are mixed with 0.13 part of water and 0.25 part of sodium carboxymethylcellulose to form protective glaze slip with the specific gravity of 1.4, and the protective glaze slip is sprayed by a high-pressure glaze spraying cabinet; wherein the chemical components of the frit comprise:
SiO 2 62.13 parts of Al 2 O 3 11.51 parts of ZrO 2 5.25 parts of Fe 2 O 3 0.12 part, 7.57 parts of CaO, 5.17 parts of MgO and K 2 O5.79 parts, na 2 O1.56 parts and loss on ignition 0.15 parts.
Then carrying out ink-jet printing, spraying overglaze, and sintering at 1250 ℃.
Through the test, no pattern yellowing phenomenon is found.
Example 8
The embodiment provides a preparation method of ceramic tiles, which comprises the following steps:
providing a ceramic body;
mixing the ceramic tile base glaze raw material in the example 4 with 0.15 part of sodium carboxymethylcellulose, 0.20 part of sodium tripolyphosphate and water to form ceramic tile base glaze slip with the specific gravity of 1.7, and then spraying the ceramic tile base glaze slip on a ceramic body by adopting a high-pressure glaze spraying cabinet;
then 11 parts of kaolin, 17 parts of potassium feldspar, 16 parts of albite, 10 parts of zirconium silicate, 7 parts of aluminum oxide, 8 parts of calcined talcum, 10 parts of quartz and 21 parts of frit are mixed with 0.13 part of water and 0.25 part of sodium carboxymethylcellulose to form protective glaze slip with the specific gravity of 1.4, and the protective glaze slip is sprayed by a high-pressure glaze spraying cabinet; wherein the chemical components of the frit comprise:
SiO 2 62.13 parts of Al 2 O 3 11.51 parts of ZrO 2 5.25 parts of Fe 2 O 3 0.12 part, 7.57 parts of CaO, 5.17 parts of MgO and K 2 O5.79 parts, na 2 O1.56 parts and loss on ignition 0.15 parts.
Then carrying out ink-jet printing, spraying overglaze, and sintering at the temperature of 1240 ℃.
Through the test, no pattern yellowing phenomenon is found.
In conclusion, the whiteness of the ceramic tile base glaze provided by the invention can meet the demand of 60-70 DEG whiteness, and can be sintered at a high temperature of 1150-1250 ℃, the glaze does not yellow, the capability of covering the blank color is strong, and the protective glaze can ensure that the inkjet printing does not yellow.
In summary, the invention provides the ceramic tile base glaze, the ceramic tile and the preparation method thereof, wherein the ceramic tile base glaze has high whiteness and is a matte glaze with stronger blank color covering capability. The ceramic tile base glaze does not need to use zirconium silicate with high price or titanium white frit, and meta-titanic acid and brucite are introduced into the ceramic tile base glaze formula to generate magnesium titanate emulsion through solid phase reaction, the glaze gloss is less than 10 ℃, and the whiteness is between 60 and 70, so that the color of a ceramic blank is covered. The ceramic tile primer provided by the invention is based on a solid phase reaction to realize the function of the primer, namely, the opacified magnesium titanate crystalline phase is synthesized through the solid phase reaction, crystallization is not needed, sintering to melting (the primer sintering) is not needed, and further, the requirement that the high-temperature viscosity of the primer after melting is low is also not met, and the primer can contain high content of aluminum oxide, so that the use of silicon-aluminum components in the primer is more relaxed than that of the primer containing titanium white frit, and the ceramic tile primer can be sintered at the high temperature of 1150-1250 ℃ by adopting the ceramic tile primer disclosed by the invention (namely, the ceramic tile primer can be used in ceramic tiles sintered at the high temperature of 1150-1250 ℃). The ceramic tile primer provided by the invention does not use titanium white frit, so that the problems of high cost, high energy consumption, limited use temperature (not high-temperature firing) and limited applicable primer formula (not used in the primer with high alumina content) caused by using the titanium white frit in the ceramic tile primer are avoided.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (10)
1. The ceramic tile base glaze is characterized by comprising the following raw materials in parts by mass:
6-12 parts of kaolin, 0-40 parts of potassium feldspar and/or albite, 5-15 parts of meta-titanic acid, 10-32 parts of brucite, 7-30 parts of talcum and 15-31 parts of low-temperature frit.
2. The ceramic tile primer according to claim 1, wherein the raw materials of the ceramic tile primer comprise the following components in parts by mass:
6-12 parts of kaolin, 7-40 parts of potassium feldspar and/or albite, 5-15 parts of meta-titanic acid, 10-32 parts of brucite, 7-30 parts of talcum and 15-31 parts of low-temperature frit.
3. The ceramic tile primer of claim 1, wherein the low temperature frit comprises the following chemical components in parts by mass:
SiO 2 55-65 parts of Al 2 O 3 6 to 12 parts of Fe 2 O 3 0 to 0.3 part, 8 to 12 parts of CaO, 0.5 to 3 parts of MgO and K 2 O2-6 parts, na 2 0.5 to 3 parts of O, 5 to 14 parts of ZnO and B 2 O 3 0.5 to 3 parts of BaO and 0 to 0.5 part of BaO.
4. The ceramic tile primer of claim 3, wherein the low temperature frit comprises the following chemical components in parts by mass:
SiO 2 55-65 parts of Al 2 O 3 6 to 12 parts of Fe 2 O 3 0.1 to 0.3 part, 8 to 12 parts of CaO, 0.5 to 3 parts of MgO and K 2 O2-6 parts, na 2 0.5 to 3 parts of O, 10 to 14 parts of ZnO and B 2 O 3 1 to 3 parts of BaO and 0.1 to 0.5 part of BaO.
5. The ceramic tile primer of any one of claims 1 to 4, wherein the raw materials of the ceramic tile primer further comprise, in parts by mass: quartz 0-15 parts.
6. A ceramic tile comprising a ceramic body, a primer layer, an inkjet decorative layer and a cover glaze layer which are sequentially laminated, wherein the primer layer is prepared from the ceramic tile primer according to any one of claims 1 to 5.
7. The ceramic tile of claim 6, further comprising:
the protective glaze layer is arranged between the ground glaze layer and the inkjet decorative layer;
the protective glaze layer is prepared from the following raw materials in parts by mass:
8-12 parts of kaolin, 10-25 parts of potassium feldspar, 10-25 parts of albite, 8-20 parts of zirconium silicate, 0-10 parts of alumina, 0-10 parts of calcined talcum, 0-15 parts of quartz and 15-30 parts of frit.
8. The ceramic tile of claim 7, wherein the frit comprises the following chemical components in parts by mass:
SiO 2 55-65 parts of Al 2 O 3 6 to 12 parts of ZrO 2 4 to 8 parts of Fe 2 O 3 0 to 0.3 part, 5 to 10 parts of CaO, 4 to 8 parts of MgO and K 2 O4-8 parts, na 2 0.5 to 3 portions of O.
9. A method of making ceramic tiles as defined in claim 6, comprising the steps of:
providing a ceramic body;
applying the ceramic tile base coat of any one of claims 1-5 to the ceramic body, then performing inkjet decoration and applying an overglaze;
firing is carried out at 1150-1250 ℃ to obtain the ceramic tile which comprises a ceramic body, a ground coat layer, an inkjet decorative layer and a surface coat layer which are sequentially laminated.
10. The method of producing ceramic tiles according to claim 9, further comprising a step of applying a protective glaze after applying the ceramic tile primer and before performing inkjet decoration, wherein the raw materials of the protective glaze include the following components in parts by mass:
8-12 parts of kaolin, 10-25 parts of potassium feldspar, 10-25 parts of albite, 8-20 parts of zirconium silicate, 0-10 parts of alumina, 0-10 parts of calcined talcum, 0-15 parts of quartz and 15-30 parts of frit.
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