CN114890670A - Bright glaze, ceramic plate and preparation method thereof - Google Patents
Bright glaze, ceramic plate and preparation method thereof Download PDFInfo
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- CN114890670A CN114890670A CN202210641863.1A CN202210641863A CN114890670A CN 114890670 A CN114890670 A CN 114890670A CN 202210641863 A CN202210641863 A CN 202210641863A CN 114890670 A CN114890670 A CN 114890670A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title description 9
- 239000013078 crystal Substances 0.000 claims abstract description 87
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 46
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 44
- 239000000126 substance Substances 0.000 claims abstract description 37
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 104
- 239000011787 zinc oxide Substances 0.000 claims description 52
- 239000002994 raw material Substances 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 14
- 239000010453 quartz Substances 0.000 claims description 14
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 14
- 239000005995 Aluminium silicate Substances 0.000 claims description 13
- 235000012211 aluminium silicate Nutrition 0.000 claims description 13
- 238000000498 ball milling Methods 0.000 claims description 13
- 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 description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000000454 talc Substances 0.000 claims description 13
- 229910052623 talc Inorganic materials 0.000 claims description 13
- 239000010456 wollastonite Substances 0.000 claims description 13
- 229910052882 wollastonite Inorganic materials 0.000 claims description 13
- 238000010304 firing Methods 0.000 claims description 12
- 239000010459 dolomite Substances 0.000 claims description 11
- 229910000514 dolomite Inorganic materials 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 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 description 10
- 230000005484 gravity Effects 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 9
- 238000005498 polishing Methods 0.000 claims description 9
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 6
- 238000007641 inkjet printing Methods 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 13
- 238000011161 development Methods 0.000 abstract description 10
- 239000000292 calcium oxide Substances 0.000 description 45
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 45
- 239000012535 impurity Substances 0.000 description 24
- 235000012239 silicon dioxide Nutrition 0.000 description 15
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 12
- 239000011521 glass Substances 0.000 description 12
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 230000018109 developmental process Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 8
- 239000000440 bentonite Substances 0.000 description 8
- 229910000278 bentonite Inorganic materials 0.000 description 8
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 239000003513 alkali Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000003373 anti-fouling effect Effects 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000010433 feldspar Substances 0.000 description 4
- 229920000609 methyl cellulose Polymers 0.000 description 4
- 239000001923 methylcellulose Substances 0.000 description 4
- 235000010981 methylcellulose Nutrition 0.000 description 4
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 235000019832 sodium triphosphate Nutrition 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000012744 reinforcing agent Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 229910052656 albite Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000010427 ball clay Substances 0.000 description 2
- 229910001570 bauxite Inorganic materials 0.000 description 2
- NWXHSRDXUJENGJ-UHFFFAOYSA-N calcium;magnesium;dioxido(oxo)silane Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O NWXHSRDXUJENGJ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 229910052637 diopside Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000007688 edging Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052903 pyrophyllite Inorganic materials 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- MQWCQFCZUNBTCM-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(SC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O MQWCQFCZUNBTCM-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052661 anorthite Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Images
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
-
- 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
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/132—Waste materials; Refuse; Residues
- C04B33/1324—Recycled material, e.g. tile dust, stone waste, spent refractory material
-
- 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
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3427—Silicates other than clay, e.g. water glass
- C04B2235/3436—Alkaline earth metal silicates, e.g. barium silicate
- C04B2235/3445—Magnesium silicates, e.g. forsterite
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3427—Silicates other than clay, e.g. water glass
- C04B2235/3436—Alkaline earth metal silicates, e.g. barium silicate
- C04B2235/3454—Calcium silicates, e.g. wollastonite
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Dispersion Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The invention provides a crystal bright glaze which comprises the following chemical components in percentage by mass: 2.3 to 63.93 percent of SiO 2 7.3 to 10.64 percent of Al 2 O 3 6.13 to 8.27 percent of CaO, 4.2 to 6.2 percent of MgO and 3.3 to 4.9 percent of K 2 O, BaO of 3.53 to 7.96 percent, SrO of 2.69 to 5.74 percent and ZnO of 3.18 to 7.3 percent. The crystal bright glaze has high surface glossiness and good transparency and texture effects, and can obviously improve the color development effect of patterns when applied to ceramic plates.
Description
Technical Field
The invention relates to the technical field of architectural ceramics, in particular to crystal bright glaze, a ceramic plate and a preparation method thereof.
Background
The traditional process of the full-polishing glazed tile is to press blank, dry, spray the ground glaze (overglaze), spray-print the pattern, spray the transparent glaze, fire, edge grind and finally polish. During the firing process of the traditional transparent glaze, partial SiO is melted 2 And Al 2 O 3 And a glass phase is generated and filled in the gaps of the carcass framework, so that the density and the transparency of the glaze layer are improved. Because the pattern texture of the fully polished glazed ceramic plate has the effect of polishing the transparent glaze layer which is covered on the fully polished glazed ceramic plate and plays a role in protection, the content of the glass phase substance of the transparent glaze layer is higherAt a high level, the transparent glass is more transparent, and the color development effect of the pattern on the lower layer is better.
The traditional transparent glaze is easy to have bad phenomena such as pinholes, bubbles and the like in the preparation process, and when the traditional transparent glaze is polished, the pinholes, the bubbles and the like are exposed outside, so that the antifouling performance does not reach the standard. In order to solve the defect, the conventional technology increases the viscosity of the glaze layer by adding a high proportion of alumina chemical components into a formula, so that the glaze layer is sealed and pressed on the glaze-polished bottom layer through bubbles, and finally, better antifouling property is ensured. Although the above technical means can achieve the antifouling property, bubbles and pinholes remain, which lowers the transparency of the glaze layer. Meanwhile, due to the existence of alumina with higher mass ratio, the glaze layer has a phenomenon of dull and heavy color and luster due to high temperature in the firing process, and the requirement of pursuing more thorough texture on the surface of the ceramic plate is also restricted.
Disclosure of Invention
Based on the crystal bright glaze, the crystal bright glaze has high surface glossiness and good feeling and texture effects, and can obviously improve the pattern color development effect when being applied to ceramic plates.
The invention is realized by the following technical scheme.
The crystal bright glaze comprises the following chemical components in percentage by mass: 52.3 to 63.93 percent of SiO 2 7.3 to 10.64 percent of Al 2 O 3 6.13 to 8.27 percent of CaO, 4.2 to 6.2 percent of MgO and 3.3 to 4.9 percent of K 2 O, BaO 3.53-7.96%, SrO 2.69-5.74% and ZnO 3.18-7.3%.
In one embodiment, SiO 2 And Al 2 O 3 The mass percentage ratio of (5.8-6.6) to (1).
In one embodiment, the sum of the mass percentages of CaO, BaO, ZnO and SrO is 23.7-28.6%.
In one embodiment, the raw materials for preparing the brilliant glaze comprise, by weight: 4 to 8 parts of kaolin, 8 to 10 parts of quartz, 36 to 40 parts of potassium feldspar, 8 to 10 parts of wollastonite, 10 to 12 parts of dolomite, 4 to 8 parts of calcined talc, 4 to 8 parts of calcined zinc oxide, 8 to 10 parts of barium sulfate and 4 to 8 parts of strontium carbonate.
In one embodiment, the raw materials for preparing the brilliant glaze further comprise a binder and a stabilizer.
The invention also provides a ceramic plate which comprises a blank layer, a ground glaze layer, an ink-jet pattern layer and a crystal bright glaze layer which are sequentially laminated, wherein the crystal bright glaze layer is made of the crystal bright glaze.
In one embodiment, the material of the green body layer is a green body, and the chemical composition of the green body comprises, by mass: 65.9 to 69.8 percent of SiO 2 19.8 to 22.9 percent of Al 2 O 3 0.4 to 0.8 percent of Fe 2 O 3 0.1 to 0.3 percent of TiO 2 1.6 to 2.1 percent of CaO, 1 to 1.5 percent of MgO and 2.9 to 3.6 percent of K 2 O and 2.3 to 3.1 percent of Na 2 O。
In one embodiment, the material of the ground coat layer is ground coat, and the ground coat comprises the following chemical compositions in percentage by mass: 56.5 to 60 percent of SiO 2 23.8 to 26 percent of Al 2 O 3 0.08 to 0.2 percent of Fe 2 O 3 0.05 to 0.14 percent of TiO 2 0.9 to 1.6 percent of CaO, 0.45 to 1.6 percent of MgO and 0.73 to 1.64 percent of K 2 O, 2.6-3.8% of Na 2 O and 7.5 to 11 percent of ZrO 2 。
In one embodiment, a protective glaze layer is further included between the ink-jet pattern layer and the crystal bright glaze layer.
The invention also provides a preparation method of the ceramic plate, which comprises the following steps:
mixing the raw materials of the bottom glaze layer with water, then carrying out ball milling, and then carrying out ageing treatment to prepare a bottom glaze; applying the ground coat to the surface of the green body layer to form the ground coat layer;
ink-jet printing is carried out on the surface of the ground coat layer to form the ink-jet pattern layer;
weighing the raw materials according to the chemical composition of the brilliant glaze, mixing the raw materials with water, ball-milling, and then carrying out aging treatment to prepare the brilliant glaze; and applying the crystal glaze material to the surface of the ink-jet pattern layer to form the crystal glaze layer, and then firing and polishing to prepare the ceramic plate.
In one embodiment, the specific gravity of the bottom glaze is 1.86g/cm 3 ～1.92g/cm 3 The glazing amount of the bottom glaze material is 440g/m 2 ～520g/m 2 ；
The specific gravity of the crystal bright glaze is 1.82g/cm 3 ～1.9g/cm 3 The glazing amount of the crystal bright glaze is 480g/m 2 ～560g/m 2 。
Compared with the prior art, the crystal bright glaze has the following beneficial effects:
according to the invention, by adding the silicon dioxide with high mass ratio into the formula of the crystal bright glaze, more glass phases can be formed, the acid and alkali resistance is better, the sintering range can be improved, and simultaneously, the high-temperature viscosity of the glass phases can be reduced to a great extent in the high-temperature reaction of the raw materials corresponding to the chemical composition BaO and SrO, so that the discharge of bubbles in the glaze layer is facilitated, the glaze layer is cleaner and more compact, and the transparency and the brightness are ensured. Moreover, the existence of ZnO, SrO and BaO high-density oxides in the formula can increase the refractive index of the glaze layer and improve the surface glossiness. The mass percentage content of CaO and BaO in the formula is far less than the corresponding chemical formula content of the condition required by actually precipitating crystals, so that the crystallization condition can not be reached and the crystallization can not be carried out. According to the invention, by screening out specific chemical compositions and proportions, the phenomenon that the glaze layer is dull and sunken due to easy crystallization in the traditional formula can be effectively eliminated, and the color development, transparency and texture effects of the glaze layer on the pattern are further improved. In addition, the crystal bright glaze provided by the invention can also have better wear resistance when being applied to ceramic plates.
Drawings
FIG. 1 is a schematic cross-sectional view of an arbitrary side of a brilliant glazed ceramic plate prepared in example 1 of the present invention;
FIG. 2 is a partial picture of a brilliant glazed ceramic panel prepared in example 1 of the present invention;
FIG. 3 is a partial picture of a brilliant glazed ceramic panel prepared in example 2 of the present invention;
FIG. 4 is a partial picture of a brilliant glazed ceramic panel prepared in example 3 of the present invention;
FIG. 5 is a partial photograph of a ceramic plate prepared in comparative example 1;
FIG. 6 is a partial picture of a brilliant glazed ceramic panel prepared in example 4 of the present invention;
FIG. 7 is a partial picture of a brilliant glazed ceramic panel prepared in example 5 of the present invention;
fig. 8 is a partial picture of a crystal glazed ceramic plate prepared in embodiment 6 of the present invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the invention, "a plurality" means at least two, e.g., two, three, etc., unless explicitly specified otherwise. In the description of the present invention, "a plurality" means at least one, e.g., one, two, etc., unless specifically limited otherwise.
The words "preferably," "more preferably," and the like, in the present disclosure mean embodiments of the disclosure that may, in some instances, provide certain benefits. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range-describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein.
The use of "including," "comprising," "containing," "having," or other variations thereof herein, is meant to encompass the non-exclusive inclusion, as such terms are not to be construed. The term "comprising" means that other steps and ingredients can be added that do not affect the end result. The term "comprising" also includes the terms "consisting of …" and "consisting essentially of …". The compositions and methods/processes of the present invention comprise, consist of, and consist essentially of the essential elements and limitations described herein, as well as any of the additional or optional ingredients, components, steps, or limitations described herein. The terms "potency", "performance", "effect" and "efficacy" are not distinguished from one another herein.
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. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The invention provides a crystal bright glaze which comprises the following chemical components in percentage by mass: 52.3 to 63.93 percent of SiO 2 7.3 to 10.64 percent of Al 2 O 3 6.13 to 8.27 percent of CaO and 4.2 percent ofMgO of 6.2 percent and K of 3.3 to 4.9 percent 2 O, BaO 3.53-7.96%, SrO 2.69-5.74% and ZnO 3.18-7.3%.
The silicon dioxide with high mass ratio in the formula can ensure that the raw materials of barium sulfate and strontium carbonate corresponding to the chemical compositions of BaO and SrO can reduce the high-temperature viscosity of a glass phase to a great extent in the high-temperature reaction with quartz, is beneficial to discharging bubbles in a glaze layer, enables the glaze layer to be cleaner and more compact, and ensures the transparency and the brightness.
Preferably, the chemical composition of the brilliant glaze comprises the following components in percentage by mass: 55.39% -56.52% of SiO 2 8.63 to 9.01 percent of Al 2 O 3 CaO 7.59-8.27%, MgO 4.4-4.66%, K4.2-4.47% 2 O, BaO of 7.12 to 7.56 percent, SrO of 4.83 to 5.28 percent and ZnO of 5.76 to 6.31 percent.
More preferably, the chemical composition of the brilliant glaze comprises, in mass percent: 55.39% SiO 2 9.01% of Al 2 O 3 7.59 percent of CaO, 4.66 percent of MgO and 4.2 percent of K 2 O, 7.56% BaO, 5.28% SrO and 6.31% ZnO.
In a specific example, the chemical composition of the brilliant glaze comprises, in mass percent: 48% -52.5% of SiO 2 6.8 to 9.5 of Al 2 O 3 6.5 to 8 percent of CaO, 3.9 to 5.8 percent of MgO and 3 to 4.5 percent of K 2 O, BaO 5.9-7.5%, SrO 4.2-5.4%, ZnO 5.5-7%, and other trace impurities 7-9.5% and ignition loss.
In one specific example, the other minor impurities are selected from 1% to 3% SO 3 In addition to P 2 O 5 、V 2 O 5 、Mu 3 O 4 、NiO、ZrO 2 、HfO 2 、Cr 2 O 3 And Rb 2 O is less than 0.01 percent.
In one specific example, SiO 2 And Al 2 O 3 The mass percentage ratio of (5.8-6.6) to (1).
As can be appreciated, inIn the present invention, SiO 2 And Al 2 O 3 Including but not limited to 5.8:1, 5.9:1, 6.0:1, 6.1:1, 6.2:1, 6.3:1, 6.4:1, 6.5:1, 6.6: 1.
High content of SiO 2 Will form more glass phase, has better acid and alkali resistance and can improve the sintering range, the SiO in the invention 2 ：Al 2 O 3 The ratio of (A) is larger, the aluminum content ratio is lower, so that the firing temperature of the glaze layer is reduced, the relative glossiness is further improved, and the texture effect is improved.
Meanwhile, because the proportion of silicon and aluminum is large and the activation capability of crystallization is low, crystals are not easy to precipitate, and in addition, the components contain 6.8-8.2 percent of CaO and 6.2-7.7 percent of BaO, the content of the flux in the formula percentage is far less than that of the actually required precipitated crystals, namely anorthite crystals CaO. Al 2 O 3 ·2SiO 2 Barium feldspar crystal BaO. Al 2 O 3 ·SiO 2 And the content of the corresponding chemical formula under the required conditions, so that the crystallization conditions can not be achieved and the crystallization can not be carried out. The formula content design also effectively eliminates the crystallization phenomenon easily caused by the conventional formula and further causes the glaze layer to be dull and heavy, thereby further improving the color development, the transparent feeling and the texture of the glaze layer on the pattern.
The selected solvent is chemical materials such as calcium oxide, barium sulfate, strontium carbonate, zinc oxide and the like, can decompose strong composite fluxing agents such as CaO, BaO, SrO, ZnO and the like at lower temperature, has quicker fluxing and better effect, is beneficial to forming more glass phase substances and increases the transparency; the fluxing agent of the traditional transparent glaze formula comprises chemical materials and mineral materials such as albite, and because the melting decomposition of the mineral materials needs higher temperature, the albite dissociates sodium oxide in a higher temperature region for fluxing, the process of forming a glass phase is slower, and the proportion of the finally formed glass phase is relatively low.
In addition, the presence of high-density oxides such as ZnO, SrO and BaO in the formulation increases the refractive index of the glaze layer, and the surface gloss is also higher.
In a specific example, the sum of the mass percentages of CaO, BaO, ZnO, and SrO is 23.7% to 28.6%.
It is understood that in the present invention, the sum of the mass percentages of CaO, BaO, ZnO, and SrO includes, but is not limited to, 23.7%, 24%, 25%, 26%, 27%, 28%, 28.6%.
In a specific example, the raw materials for preparing the brilliant glaze comprise, by weight: 4 to 8 parts of kaolin, 8 to 10 parts of quartz, 36 to 40 parts of potassium feldspar, 8 to 10 parts of wollastonite, 10 to 12 parts of dolomite, 4 to 8 parts of calcined talc, 4 to 8 parts of calcined zinc oxide, 8 to 10 parts of barium sulfate and 4 to 8 parts of strontium carbonate.
In a specific example, the raw materials for preparing the brilliant glaze further comprise a binder and a stabilizer.
More specifically, the binder is methylcellulose.
More specifically, the stabilizer is sodium tripolyphosphate.
In a specific example, the raw materials for preparing the brilliant glaze comprise the following components in parts by weight: 4 to 8 parts of kaolin, 8 to 10 parts of quartz, 36 to 40 parts of potassium feldspar, 8 to 10 parts of wollastonite, 10 to 12 parts of dolomite, 4 to 8 parts of calcined talc, 4 to 8 parts of calcined zinc oxide, 8 to 10 parts of barium sulfate, 4 to 8 parts of strontium carbonate, 24 to 30 parts of water, 0.1 to 0.2 part of methylcellulose and 0.3 to 0.4 part of sodium tripolyphosphate.
The invention also provides a ceramic plate which comprises a blank layer, a ground glaze layer, an ink-jet pattern layer and a crystal bright glaze layer which are sequentially laminated, wherein the crystal bright glaze layer is made of the crystal bright glaze.
The ceramic plate provided by the invention has a glittering and translucent surface, and has the advantages of good pattern color development, strong transparency, no surface defect, acid and alkali resistance and the like.
In a specific example, the material of the green body layer is a green body, and the chemical composition of the green body comprises the following components in percentage by mass: 65.9 to 69.8 percent of SiO 2 19.8 to 22.9 percent of Al 2 O 3 0.4 to 0.8 percent of Fe 2 O 3 、0.1％～0.3% TiO 2 1.6 to 2.1 percent of CaO, 1 to 1.5 percent of MgO and 2.9 to 3.6 percent of K 2 O and 2.3 to 3.1 percent of Na 2 O。
In a specific example, the material of the ground coat is ground coat, and the chemical composition of the ground coat comprises the following components in percentage by mass: 56.5 to 60 percent of SiO 2 23.8 to 26 percent of Al 2 O 3 0.08 to 0.2 percent of Fe 2 O 3 0.05 to 0.14 percent of TiO 2 0.9 to 1.6 percent of CaO, 0.45 to 1.6 percent of MgO and 0.73 to 1.64 percent of K 2 O, 2.6-3.8% of Na 2 O and 7.5 to 11 percent of ZrO 2 。
In a specific example, the raw materials for preparing the green body comprise, by weight: 23 to 28 parts of ball clay, 9 to 12 parts of calcined coal gangue, 11 to 14 parts of sodium potassium abrasive, 8 to 10 parts of sodium potassium powder, 2 to 4 parts of polishing mud, 5 to 7 parts of medium temperature sand, 3 to 6 parts of bauxite, 3 to 5 parts of pyrophyllite, 4 to 6 parts of bentonite, 4 to 7 parts of diopside, 2 to 4 parts of high clay, 10 to 13 parts of sand paste, 0.2 to 0.4 part of dispergator, 0.2 to 0.4 part of aqua alkalium and 0.3 to 0.5 part of reinforcing agent.
In a specific example, the raw materials for preparing the ground coat comprise, by weight: 38 to 42 parts of feldspar, 10 to 12 parts of kaolin, 28 to 34 parts of quartz, 8 to 12 parts of calcined talc, 5 to 7 parts of wollastonite and 1 to 3 parts of bentonite.
According to the crystal bright glazed ceramic board provided by the technical scheme, a proper amount of bentonite is added into the raw materials of the blank layer and the ground glaze layer, and due to the characteristics of cohesiveness, plasticity, nodularity, suspension property and the like of the bentonite, the plasticity and strength of the blank and the glaze can be increased, so that the lubricating effect is increased, the ball milling of glaze slip is facilitated, and in addition, the suspension property and stability are enhanced, so that the crystal bright glazed ceramic board has the advantages of fine texture, smooth glazed skin, good transmittance, collision resistance, good mechanical strength and the like. The process of decomposing bentonite into mullite in the green body is a process of forming a green body frame, the firing temperature range can be widened in the process, the ceramic green body is not easy to deform and lose shape, the whiteness and the stability are improved, and the high bonding strength and the bending resistance are provided for a final product; the bentonite is added into the ground glaze to play the roles of a plasticizer and a thickening agent, so that the strength, plasticity, high adhesiveness and whiteness can be provided for the glaze and a support; the combination of the blank body, the ground glaze and the crystal bright glaze can better realize the integration of the blank glaze, and the density is high after the high-temperature melting, the surface of the glaze layer is smooth and free of defects after sintering, the glaze surface is strong in permeability, and the pattern color is good.
In a specific example, a protective glaze layer is further included between the inkjet pattern layer and the crystal glaze layer.
The invention also provides a preparation method of the ceramic plate, which comprises the following steps:
mixing the raw materials of the bottom glaze layer with water, then carrying out ball milling, and then carrying out ageing treatment to prepare a bottom glaze; applying a ground glaze material to the surface of the green body layer to form a ground glaze layer;
performing ink-jet printing on the surface of the ground coat layer to form an ink-jet pattern layer;
weighing raw materials according to the chemical composition of the brilliant glaze, mixing the raw materials with water, ball-milling, and then carrying out aging treatment to prepare the brilliant glaze; and applying the crystal glaze material to the surface of the ink-jet pattern layer to form a crystal glaze layer, and then firing and polishing to prepare the ceramic plate.
In one specific example, the maximum firing temperature is 1160 ℃ to 1220 ℃.
In one specific example, the specific gravity of the base frit is 1.86g/cm 3 ～1.92g/cm 3 The glazing amount of the base glaze is 440g/m 2 ～520g/m 2 。
It is understood that, in the present invention, the specific gravity of the ground glaze includes, but is not limited to, 1.86g/cm 3 、1.87g/cm 3 、1.88g/cm 3 、1.89g/cm 3 、1.9g/cm 3 、1.91g/cm 3 、1.92g/cm 3 . It is understood that, in the present invention, the amount of the glaze applied to the base glaze includes, but is not limited to, 440g/m 2 、450g/m 2 、460g/m 2 、470g/m 2 、480g/m 2 、490g/m 2 、500g/m 2 、510g/m 2 、520g/m 2 。
In one specific example, the specific gravity of the brilliant glaze is 1.82g/cm 3 ～1.9g/cm 3 The glazing amount of the crystal glaze is 480g/m 2 ～560g/m 2 。
It is understood that, in the present invention, the specific gravity of the brilliant glaze includes, but is not limited to, 1.82g/cm 3 、1.83g/cm 3 、1.84g/cm 3 、1.85g/cm 3 、1.86g/cm 3 、1.87g/cm 3 、1.88g/cm 3 、1.89g/cm 3 、1.9g/cm 3 . It is understood that in the present invention, the glazing amount of the brilliant glaze includes, but is not limited to, 480g/m 2 、490g/m 2 、500g/m 2 、510g/m 2 、520g/m 2 、530g/m 2 、540g/m 2 、550g/m 2 、560g/m 2 。
In a more specific example, the method for preparing the ceramic plate comprises the following steps:
mixing the raw materials of the green body layer with water, then ball-milling, preparing a green body material through a spray tower, and performing compression molding and drying to prepare the green body layer;
mixing the raw materials of the bottom glaze layer with water, then carrying out ball milling, and then carrying out ageing treatment to prepare a bottom glaze; applying a ground glaze material to the surface of the green body layer to form a ground glaze layer;
performing ink-jet printing on the surface of the ground coat layer to form an ink-jet pattern layer;
spraying protective glaze on the surface of the ink-jet pattern layer to form a protective glaze layer;
weighing raw materials according to the chemical composition of the brilliant glaze, mixing the raw materials with water, ball-milling, and then carrying out aging treatment to prepare the brilliant glaze; and applying crystal bright glaze to the surface of the protective glaze layer to form a crystal bright glaze layer, and then firing, polishing and edging to prepare the ceramic plate.
The crystal glaze, the ceramic plate and the preparation method thereof according to the present invention will be further described in detail with reference to the following specific examples. The starting materials used in the following examples are all commercially available products unless otherwise specified.
Example 1
The embodiment provides a crystal bright glazed ceramic plate, which specifically comprises the following components:
(1) preparing a blank body: weighing the raw materials according to the components of the blank layer raw materials, and uniformly mixing: 25.5 parts of ball clay, 10.5 parts of calcined coal gangue, 12.5 parts of potassium-sodium water grinding material, 9 parts of potassium-sodium stone powder, 3 parts of polishing mud material, 6 parts of medium temperature sand, 4.5 parts of bauxite, 4 parts of pyrophyllite, 5 parts of bentonite, 5.5 parts of diopside, 3 parts of high clay, 11.5 parts of sand paste, 0.3 part of dispergator, 0.3 part of alkali water agent and 0.4 part of reinforcing agent; the debonder is DuramaxD-3019, the alkali water agent is sodium silicate, and the reinforcing agent is vinyl acetate; mixing the uniformly mixed raw materials and water according to the mass ratio of 3:1, adding the mixture into a ball mill for ball milling, and preparing a blank material through a spray tower after ball milling, wherein the mass percent of the water of the blank material is 6-7%, the particle size of the blank material is more than 95% after passing through a 100-mesh screen, and then, placing the blank material under a hydraulic press, and performing compression molding and drying under the pressure of 300bar to obtain a blank; wherein the blank layer comprises the following chemical components in percentage by mass: SiO 2 2 67.8％、Al 2 O 3 21.3％、Fe 2 O 3 0.6％、TiO 2 0.2％、CaO 1.8％、MgO 1.2％、K 2 O 3.3％、Na 2 O 2.7％；
(2) Preparing a base coat: weighing the following components according to the composition of the raw materials of the ground glaze layer: 40 parts of feldspar, 11 parts of kaolin, 31 parts of quartz, 10 parts of calcined talc, 6 parts of wollastonite and 2 parts of bentonite, taking 100 parts of mixed raw materials, then adding 27 parts of water, 0.15 part of methylcellulose and 0.35 part of sodium tripolyphosphate, ball-milling for 5-8 hours, sieving by a 325-mesh sieve to obtain 0.3-0.7% of screen residue, then sieving by the 325-mesh sieve and ageing for 24-48 hours to obtain a ground glaze; the ground coat layer comprises the following chemical components in percentage by mass: SiO 2 2 58.2％、Al 2 O 3 24.8％、Fe 2 O 3 0.14％、TiO 2 0.1％、CaO 1.2％、MgO 0.9％、K 2 O 1.2％、Na 2 O 3.2％、ZrO 2 9%, the ignition loss and trace impurities were 1.5%.
(3) Crystal bright glazeThe preparation of (1): weighing the following components according to the components of the raw material of the brilliant glaze: 6 parts of kaolin, 9 parts of quartz, 38 parts of potash feldspar, 9 parts of wollastonite, 11 parts of dolomite, 6 parts of calcined talc, 6 parts of calcined zinc oxide, 9 parts of barium carbonate and 6 parts of strontium carbonate, wherein the mixed raw materials are 100 parts, 27 parts of water, 0.15 part of methyl cellulose and 0.35 part of sodium tripolyphosphate are added, the mixture is ball-milled for 5 to 8 hours and is sieved by a 325-mesh sieve, the measured screen residue is 0.3 to 0.7 percent, and the mixture is sieved by the 325-mesh sieve and is aged for 24 to 48 hours to obtain brilliant glaze; wherein, the ignition loss value and trace impurities are included, and the crystal bright glaze comprises the following components in percentage by mass: SiO 2 2 50.54％、Al 2 O 3 8.22％、CaO 6.92％、MgO 4.25％、K 2 3.83 percent of O, 6.9 percent of BaO, 4.82 percent of SrO, 5.76 percent of ZnO, and 8.76 percent of ignition loss value and trace impurities;
the crystal bright glaze does not comprise a ignition loss value and trace impurities, and comprises the following chemical compositions in percentage by mass: SiO 2 2 55.39、Al 2 O 3 9.01％、CaO 7.59％、MgO 4.66％、K 2 O 4.2％、BaO 7.56％、SrO 5.28％、ZnO 6.31％。SiO 2 With Al 2 O 3 The mass percentage ratio of the CaO, the BaO, the ZnO and the SrO is 6.15:1, and the sum of the mass percentages of the CaO, the BaO, the ZnO and the SrO is 26.74 percent;
(4) preparing a ground glaze layer: applying a ground coat on the green body layer, wherein the specific gravity of the ground coat is 1.89g/m 3 The glazing amount is 490g/m 2 (ii) a (5) Preparation of ink-jet pattern layer: ink-jet printing on the surface with the ground coat;
(6) preparing a crystal bright glaze layer: applying crystal bright glaze on the ink-jet pattern layer, wherein the specific gravity of the crystal bright glaze is 1.86g/m 3 The glazing amount is 520g/m 2 ；
(7) Firing: firing for 70 minutes in a kiln with the highest firing temperature of 1160-1220 ℃ to form a semi-finished product, and then polishing and edging to obtain a crystal glaze ceramic plate;
the prepared brilliant glaze ceramic plate is cut at any side, as shown in figure 1. As can be seen in fig. 1, wherein the green body layer is marked as 1 and represents a plate, the ground glaze layer is marked as 2 and represents a plate, the ink-jet pattern layer is marked as 3 and represents a crystal glaze layer is marked as 4 and represents a plate;
the partial view of the prepared crystal glazed ceramic plate is shown in fig. 2, and it can be seen from the figure that the crystal glazed ceramic plate prepared by the embodiment has a crystal clear and transparent surface, and has the characteristics of good pattern color development, strong transparency, no surface defect and the like.
Example 2
The embodiment provides a crystal bright glazed ceramic plate, which specifically comprises the following components:
the difference between the present embodiment and embodiment 1 is that the crystal bright glaze of the present embodiment comprises the following raw materials: 7 parts of kaolin, 11.5 parts of quartz, 34.5 parts of potassium feldspar, 10 parts of wollastonite, 12 parts of dolomite, 5.5 parts of calcined talc, 5.5 parts of calcined zinc oxide, 8.5 parts of barium sulfate and 5.5 parts of strontium carbonate;
the ignition loss value and trace impurities are included, and the brilliant glaze comprises the following components in percentage by weight: SiO 2 2 51.8％、Al 2 O 3 7.91％、CaO 7.58％、MgO 4.03％、K 2 4.1 percent of O, 6.52 percent of BaO, 4.43 percent of SrO4, 5.28 percent of ZnO, 8.35 percent of ignition loss and trace impurities.
The crystal bright glaze does not comprise a ignition loss value and trace impurities, and comprises the following chemical compositions in percentage by mass: SiO 2 2 56.52％、Al 2 O 3 8.63％、CaO 8.27％、MgO 4.4％、K 2 O 4.47％、BaO 7.12％、SrO 4.83％、ZnO 5.76％。SiO 2 With Al 2 O 3 The mass percentage ratio of CaO, BaO, ZnO and SrO is 6.55:1, and the sum of the mass percentages of CaO, BaO, ZnO and SrO is 25.98%.
A partial picture of the crystal glazed ceramic plate prepared in this example is shown in fig. 3.
Example 3
The embodiment provides a crystal bright glazed ceramic plate, which specifically comprises the following components:
the difference between the present embodiment and embodiment 1 is that the crystal bright glaze of the present embodiment comprises the following raw materials: 5 parts of kaolin, 10 parts of quartz, 39.5 parts of potassium feldspar, 7 parts of wollastonite, 9.5 parts of dolomite, 6.5 parts of calcined talc, 6.5 parts of calcined zinc oxide, 9.5 parts of barium sulfate and 6.5 parts of strontium carbonate;
the ignition loss value and trace impurities are included, and the brilliant glaze comprises the following components in percentage by weight: SiO 2 2 50.69％、Al 2 O 3 8.57％、CaO 6％、MgO 4.47％、K 2 3.96% of O, 7.38% of BaO, 5.32% of SrO, 6.34% of ZnO, 7.27% of ignition loss and trace impurities.
The crystal bright glaze does not comprise a ignition loss value and trace impurities, and comprises the following chemical compositions in percentage by mass: SiO 2 2 54.66％、Al 2 O 3 9.24％、CaO 6.47％、MgO 4.82％、K 2 O 4.27％、BaO 7.96％、SrO 5.74％、ZnO 6.84％。SiO 2 With Al 2 O 3 The mass percentage ratio of the component (A) to the component (B) is 5.92:1, and the sum of the mass percentages of CaO, BaO, ZnO and SrO is 27.01%.
A partial picture of the crystal glazed ceramic plate prepared in this example is shown in fig. 4.
Example 4
The embodiment provides a crystal bright glazed ceramic plate, which specifically comprises the following components:
the difference between the present embodiment and embodiment 1 is that the crystal bright glaze of the present embodiment comprises the following raw materials: 7 parts of kaolin, 10 parts of quartz, 41 parts of potassium feldspar, wollastonite, 10 parts of dolomite, 5 parts of calcined talc, 6 parts of calcined zinc oxide, 9 parts of barium carbonate and 6 parts of strontium carbonate;
the ignition loss value and trace impurities are included, and the brilliant glaze comprises the following components in percentage by weight: SiO 2 2 50.36％、Al 2 O 3 9.03％、CaO 6.3％、MgO 4.27％、K 2 4.03 percent of O, 6.9 percent of BaO6, 4.82 percent of SrO, 5.76 percent of ZnO, and 8.53 percent of ignition loss value and trace impurities.
The crystal bright glaze does not comprise a ignition loss value and trace impurities, and comprises the following chemical compositions in percentage by mass: SiO 2 2 55.06％、Al 2 O 3 9.87％、CaO 6.89％、MgO 4.67％、K 2 O 4.4％、BaO 7.54％、SrO 5.27％、ZnO 6.3％。SiO 2 With Al 2 O 3 The mass percentage ratio of the CaO, the BaO, the ZnO and the SrO is 5.58:1, and the sum of the mass percentages of the CaO, the BaO, the ZnO and the SrO is 26 percent.
A partial picture of the crystal glazed ceramic plate prepared in this example is shown in fig. 6.
Example 5
The embodiment provides a crystal bright glazed ceramic plate, which specifically comprises the following components:
the difference between the present embodiment and embodiment 1 is that the crystal bright glaze of the present embodiment comprises the following raw materials: 6 parts of kaolin, 14 parts of quartz, 33 parts of potassium feldspar, 11 parts of wollastonite, 10 parts of dolomite, 5 parts of calcined talc, 6 parts of calcined zinc oxide, 9 parts of barium carbonate and 6 parts of strontium carbonate;
the ignition loss value and trace impurities are included, and the brilliant glaze comprises the following components in percentage by weight: SiO 2 2 52.47％、Al 2 O 3 7.72％、CaO 6.3％、MgO 4.27％、K 2 3.32 percent of O, 6.9 percent of BaO, 4.82 percent of SrO, 5.76 percent of ZnO, and 8.44 percent of ignition loss value and trace impurities.
The crystal bright glaze does not comprise a ignition loss value and trace impurities, and comprises the following chemical compositions in percentage by mass: SiO 2 2 57.31％、Al 2 O 3 8.43％、CaO 6.88％、MgO 4.66％、K 2 O 3.63％、BaO 7.54％、SrO 5.26％、ZnO 6.29％。SiO 2 With Al 2 O 3 The mass percentage ratio of CaO, BaO, ZnO and SrO is 6.8:1, and the sum of the mass percentages of CaO, BaO, ZnO and SrO is 25.97%.
A partial picture of the crystal glazed ceramic plate prepared in this example is shown in fig. 7.
Example 6
The embodiment provides a crystal bright glazed ceramic plate, which specifically comprises the following components:
the difference between the present embodiment and embodiment 1 is that the crystal bright glaze of the present embodiment comprises the following raw materials: 7 parts of kaolin, 16 parts of quartz, 40 parts of potassium feldspar, 11 parts of wollastonite, 9 parts of dolomite, 7 parts of calcined talc, 3 parts of calcined zinc oxide, 4 parts of barium carbonate and 3 parts of strontium carbonate;
the ignition loss value and trace impurities are included, and the brilliant glaze comprises the following components in percentage by weight: SiO 2 2 57.86％、Al 2 O 3 9.63％、CaO 5.55％、MgO 4.96％、K 2 O4%, BaO 3.19%, SrO 2.43%, ZnO 2.88%, and the ignition loss value and trace impurities are 9.5%.
The crystal bright glaze does not comprise a ignition loss value and trace impurities, and comprises the following chemical compositions in percentage by mass: SiO 2 2 63.93％、Al 2 O 3 10.64％、CaO 6.13％、MgO 5.48％、K 2 O 4.42％、BaO 3.53％、SrO 2.69％、ZnO 3.18％。SiO 2 With Al 2 O 3 The mass percentage ratio of CaO, BaO, ZnO and SrO is 6.0:1, and the sum of the mass percentages of CaO, BaO, ZnO and SrO is 15.53 percent.
A partial picture of the crystal glaze ceramic plate prepared in this example is shown in fig. 8.
Comparative example 1
The comparative example provides a crystal bright glazed ceramic plate, which specifically comprises the following components:
the comparative example is different from example 1 in that the raw materials of the comparative example comprise the following components: 6 parts of kaolin, 9 parts of quartz, 38 parts of potassium feldspar, 9 parts of wollastonite, 11 parts of dolomite, 6 parts of calcined talc, 6 parts of calcined zinc oxide, 9 parts of barium sulfate and 6 parts of sodium carbonate;
the ignition loss value and trace impurities are included, and the composition comprises the following components in percentage by weight: SiO 2 2 50.54％、Al 2 O 3 8.22％、CaO 6.92％、MgO 4.25％、K 2 O 3.83％、Na 2 4.82 percent of O, 6.9 percent of BaO, 5.76 percent of ZnO, 8.76 percent of ignition loss and trace impurities.
The crystal bright glaze does not comprise a ignition loss value and trace impurities, and comprises the following chemical compositions in percentage by mass: SiO 2 2 55.39％、Al 2 O 3 9.01％、CaO 7.59％、MgO 4.66％、K 2 O 4.2％、Na 2 O 5.28％、BaO 7.56％、ZnO 6.31％。SiO 2 With Al 2 O 3 The mass percentage ratio of (A) is 26.74.
A partial picture of the crystal bright glazed ceramic plate prepared by the comparative example is shown in fig. 5.
Effect characterization
The ceramic sheets prepared in examples 1 to 6 and comparative example 1 were tested for surface stain resistance, abrasion resistance and surface quality using the method of GB/T3810.14, and for gloss using a gloss meter, and the results are shown in the following table:
table 1 table for testing properties of products prepared in examples 1 to 6 and comparative example 1
As can be seen from the data of example 1 and comparative example 1, when strontium carbonate was replaced with sodium carbonate in the raw material, pinholes were relatively conspicuous on the sheet surface
The strontium carbonate introduced by the invention can reduce the opacification phenomenon caused by crystallization to a certain extent, is beneficial to forming more glass phase substances, increases the transparency and color development effect and improves the antifouling performance.
As can be seen from the data in the above examples 1-3, the brightness of the crystal bright overglaze ceramic plate prepared by the technical scheme of the invention is between 93 and 96 degrees, the pollution resistance reaches over 5 grades, the crystal bright overglaze ceramic plate has excellent wear resistance reaching over 3 grades, no pinholes exist,
The surface glossiness is high, the permeability is strong, the color development is good, the quality is excellent, and the like. As can be seen from the data of examples 1 and 4, when SiO 2 With Al 2 O 3 When the mass percentage ratio of the aluminum oxide is too small, the aluminum oxide content is relatively large in the formula ratio, melting at a higher temperature is needed, the glossiness value is obviously reduced, and the transparent feeling and color development effects are general; as can be seen from the data of examples 1 and 5, when SiO 2 With Al 2 O 3 When the mass percentage ratio of (A) is too large, namely the content of alumina is relatively small in the formula ratio, the wear resistance and hardness of the aluminum alloy are relatively reduced; it can be seen from the data of examples 1 and 6 that when the sum of the mass percentages of CaO, BaO, ZnO and SrO is too small, the fluxing process is slow, and accordingly the formation of the glass phase is slow, resulting in a lower surface gloss, a dull glaze and less transparent feel.
The content ratio range of the silicon oxide and the aluminum oxide and the sum of the mass percentages of the CaO, the BaO, the ZnO and the SrO in the technical scheme provided by the invention are mutually synergistic and effective.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, so as to understand the technical solutions of the present invention specifically and in detail, but not to be understood as the limitation of the protection scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the appended claims. Therefore, the protection scope of the present invention should be subject to the content of the appended claims, and the description and the drawings can be used for explaining the content of the claims.
Claims (10)
1. The crystal bright glaze is characterized by comprising the following chemical components in percentage by mass: 52.3 to 63.93 percent of SiO 2 7.3 to 10.64 percent of Al 2 O 3 6.13% -8.27% of CaO, 4.2% -6.2% of MgO, 3.3% -E4.9% of K 2 O, BaO 3.53-7.96%, SrO 2.69-5.74% and ZnO 3.18-7.3%.
2. The brilliant glaze of claim 1, wherein SiO 2 And Al 2 O 3 The mass percentage ratio of (5.8-6.6): 1.
3. The brilliant glaze according to claim 1, wherein the sum of the mass percentages of CaO, BaO, ZnO and SrO is 23.7-28.6%.
4. The crystal bright glaze according to any one of claims 1 to 3, wherein the raw materials for preparing the crystal bright glaze comprise, by weight: 4 to 8 parts of kaolin, 8 to 10 parts of quartz, 36 to 40 parts of potassium feldspar, 8 to 10 parts of wollastonite, 10 to 12 parts of dolomite, 4 to 8 parts of calcined talc, 4 to 8 parts of calcined zinc oxide, 8 to 10 parts of barium sulfate and 4 to 8 parts of strontium carbonate.
5. The crystal bright glaze according to claim 4, wherein the raw materials for preparing the crystal bright glaze further comprise a binder and a stabilizer.
6. A ceramic plate characterized by comprising a green body layer, a ground coat layer, an ink-jet pattern layer and a crystal glaze layer which are laminated in this order, wherein the crystal glaze layer is made of the crystal glaze according to any one of claims 1 to 5.
7. The ceramic panel according to claim 6, wherein the material of the green body layer is a green body, and the chemical composition of the green body comprises, in mass percent: 65.9 to 69.8 percent of SiO 2 19.8 to 22.9 percent of Al 2 O 3 0.4 to 0.8 percent of Fe 2 O 3 0.1 to 0.3 percent of TiO 2 1.6 to 2.1 percent of CaO, 1 to 1.5 percent of MgO and 2.9 to 3.6 percent of K 2 O and 2.3 to 3.1 percent of Na 2 O。
8. The ceramic panel as claimed in claim 6, wherein the material of the ground glaze layer is a ground glaze, and the chemical composition of the ground glaze comprises, in mass percent: 56.5 to 60 percent of SiO 2 23.8 to 26 percent of Al 2 O 3 0.08 to 0.2 percent of Fe 2 O 3 0.05 to 0.14 percent of TiO 2 0.9 to 1.6 percent of CaO, 0.45 to 1.6 percent of MgO and 0.73 to 1.64 percent of K 2 O, 2.6-3.8% of Na 2 O and 7.5 to 11 percent of ZrO 2 。
9. The ceramic plate according to any one of claims 6 to 8, wherein a protective glaze layer is further included between the inkjet pattern layer and the crystal glaze layer.
10. A method for preparing a ceramic plate according to any one of claims 6 to 9, comprising the steps of:
mixing the raw materials of the bottom glaze layer with water, then carrying out ball milling, and then carrying out ageing treatment to prepare a bottom glaze; applying the ground coat to the surface of the green body layer to form the ground coat layer;
ink-jet printing is carried out on the surface of the ground coat layer to form the ink-jet pattern layer;
weighing raw materials according to the chemical composition of the brilliant glaze of any one of claims 1 to 5, mixing the raw materials with water, ball-milling the mixture, and then carrying out aging treatment to prepare the brilliant glaze; applying the crystal glaze material to the surface of the ink-jet pattern layer to form the crystal glaze layer, and then firing and polishing to prepare the ceramic plate;
wherein the specific gravity of the bottom glaze is 1.86g/cm 3 ～1.92g/cm 3 The glazing amount of the bottom glaze material is 440g/m 2 ～520g/m 2 ；
The specific gravity of the crystal bright glaze is 1.82g/cm 3 ～1.9g/cm 3 The glazing amount of the crystal bright glaze is 480g/m 2 ～560g/m 2 。
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110885189A (en) * | 2019-11-13 | 2020-03-17 | 蒙娜丽莎集团股份有限公司 | Zirconium-free mutton tallow glaze and positioning crystal pattern ceramic tile prepared from same |
| CN111689769A (en) * | 2020-06-28 | 2020-09-22 | 广西美尔奇建材有限公司 | Porcelain archaized brick with silk surface and preparation method thereof |
| CN112707644A (en) * | 2020-12-24 | 2021-04-27 | 肇庆乐华陶瓷洁具有限公司 | Low-gloss transparent glaze, ceramic tile using same and preparation method thereof |
| CN113999054A (en) * | 2021-10-12 | 2022-02-01 | 广东清远蒙娜丽莎建陶有限公司 | Crystal-drilled marble porcelain tile and preparation method thereof |
| CN114195496A (en) * | 2021-11-29 | 2022-03-18 | 广东德利丰家居有限公司 | Preparation method of terrazzo-like ceramic plate with concave-convex texture and ceramic plate |
| CN114276016A (en) * | 2021-12-30 | 2022-04-05 | 广东萨米特陶瓷有限公司 | Soft glaze, soft glaze ceramic rock plate and preparation method thereof |
-
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110885189A (en) * | 2019-11-13 | 2020-03-17 | 蒙娜丽莎集团股份有限公司 | Zirconium-free mutton tallow glaze and positioning crystal pattern ceramic tile prepared from same |
| CN111689769A (en) * | 2020-06-28 | 2020-09-22 | 广西美尔奇建材有限公司 | Porcelain archaized brick with silk surface and preparation method thereof |
| CN112707644A (en) * | 2020-12-24 | 2021-04-27 | 肇庆乐华陶瓷洁具有限公司 | Low-gloss transparent glaze, ceramic tile using same and preparation method thereof |
| CN113999054A (en) * | 2021-10-12 | 2022-02-01 | 广东清远蒙娜丽莎建陶有限公司 | Crystal-drilled marble porcelain tile and preparation method thereof |
| CN114195496A (en) * | 2021-11-29 | 2022-03-18 | 广东德利丰家居有限公司 | Preparation method of terrazzo-like ceramic plate with concave-convex texture and ceramic plate |
| CN114276016A (en) * | 2021-12-30 | 2022-04-05 | 广东萨米特陶瓷有限公司 | Soft glaze, soft glaze ceramic rock plate and preparation method thereof |
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