CN116813384A - Low-expansion cordierite crystal wear-resistant full-polished glazed ceramic tile and preparation method thereof - Google Patents
Low-expansion cordierite crystal wear-resistant full-polished glazed ceramic tile and preparation method thereof Download PDFInfo
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- CN116813384A CN116813384A CN202310613167.4A CN202310613167A CN116813384A CN 116813384 A CN116813384 A CN 116813384A CN 202310613167 A CN202310613167 A CN 202310613167A CN 116813384 A CN116813384 A CN 116813384A
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- glaze
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- resistant full
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- 239000000919 ceramic Substances 0.000 title claims abstract description 48
- 229910052878 cordierite Inorganic materials 0.000 title claims abstract description 44
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000013078 crystal Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011449 brick Substances 0.000 claims abstract description 31
- 238000005498 polishing Methods 0.000 claims abstract description 24
- 238000010304 firing Methods 0.000 claims abstract description 13
- 238000007639 printing Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 21
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 16
- 229910052796 boron Inorganic materials 0.000 claims description 16
- 238000002844 melting Methods 0.000 claims description 16
- 230000008018 melting Effects 0.000 claims description 16
- 238000005507 spraying Methods 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 10
- 230000005484 gravity Effects 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- 238000005299 abrasion Methods 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 34
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 24
- 239000000395 magnesium oxide Substances 0.000 description 17
- 235000012245 magnesium oxide Nutrition 0.000 description 17
- 239000011787 zinc oxide Substances 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 239000011734 sodium Substances 0.000 description 10
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000001506 calcium phosphate Substances 0.000 description 6
- 235000011010 calcium phosphates Nutrition 0.000 description 6
- 239000004927 clay Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 230000035515 penetration Effects 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical class [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 6
- 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 description 5
- 229910000389 calcium phosphate Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000007373 indentation Methods 0.000 description 5
- 239000000454 talc Substances 0.000 description 5
- 229910052623 talc Inorganic materials 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 229910052656 albite Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- QYHKLBKLFBZGAI-UHFFFAOYSA-N boron magnesium Chemical compound [B].[Mg] QYHKLBKLFBZGAI-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000007641 inkjet printing Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- -1 oxygen ion Chemical class 0.000 description 3
- 239000011435 rock Substances 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000005341 toughened glass Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241001270131 Agaricus moelleri Species 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 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
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052928 kieserite Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- 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
-
- 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
- C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
- C04B35/195—Alkaline earth aluminosilicates, e.g. cordierite or anorthite
-
- 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
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- 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
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
- C04B2235/3409—Boron oxide, borates, boric acids, or oxide forming salts thereof, e.g. borax
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
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- 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
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- Chemical Kinetics & Catalysis (AREA)
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- Geochemistry & Mineralogy (AREA)
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- Manufacturing & Machinery (AREA)
- Glass Compositions (AREA)
Abstract
The invention relates to a low-expansion cordierite crystal wear-resistant full-polished glazed ceramic tile and a preparation method thereof. The preparation method of the low-expansion cordierite crystal wear-resistant full-polished glazed ceramic tile comprises the following steps: applying surface glaze on the surface of the green brick; printing patterns on the surface of the green bricks after the overglaze is applied in an inkjet mode; applying a first low-expansion wear-resistant full-polished glaze on the surface of the green brick after the pattern is printed by ink jet; applying a second low-expansion wear-resistant full-polishing glaze on the surface of the blank body to which the first low-expansion wear-resistant full-polishing glaze is applied; and firing to obtain the low-expansion cordierite crystal wear-resistant full-polished glazed ceramic tile.
Description
Technical Field
The invention relates to a low-expansion cordierite crystal wear-resistant full-polished glazed ceramic tile and a preparation method thereof, and belongs to the technical field of ceramic tile production and manufacturing.
Background
The traditional ceramic body formula mainly comprises a Si-Al-K-Na formula system, quartz, mullite and glass phases are mainly formed after the formula system is fired, and the expansion coefficient of the body is higher (8-10 multiplied by 10) -6 /K). The CJ/T157-2017 'household gas cooker application layer toughened glass panel' is used for detecting that the ceramic plate fired by the traditional blank formula is cracked once, and the thermal shock resistance is poor.
Currently, the low-expansion ceramic rock plate has low expansion coefficient and good thermal shock resistance, and can be used for stoves, gas stove panels and the like. However, because the expansion coefficient of the low-expansion ceramic rock plate blank is low, and the expansion coefficient of the existing glaze is generally larger, the existing glaze with high expansion coefficient cannot be well matched with the low-expansion ceramic rock plate blank, and only a mode of reducing the glaze spraying amount of digital glaze is often adopted to prepare matte series products.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a low-expansion cordierite crystal wear-resistant full-polished ceramic tile and a preparation method thereof.
In a first aspect, the invention provides a method for preparing a low-expansion cordierite crystal wear-resistant full-polished glazed ceramic tile, comprising the following steps:
applying surface glaze on the surface of the green brick;
printing patterns on the surface of the green bricks after the overglaze is applied in an inkjet mode;
applying a first low-expansion wear-resistant full-polished glaze on the surface of the green brick after the pattern is printed by ink jet;
applying a second low-expansion wear-resistant full-polishing glaze on the surface of the blank body to which the first low-expansion wear-resistant full-polishing glaze is applied;
and firing to obtain the low-expansion cordierite crystal wear-resistant full-polished glazed ceramic tile.
Preferably, the chemical composition of the raw materials of the green brick comprises: in mass percent，IL：4-6％、SiO 2 ：45-50％、Al 2 O 3 ：25-32％、Fe 2 O 3 ：0.1-0.5％、TiO 2 ：0.1-0.5％、CaO：1-2％、MgO：9-12％、K 2 O：0.5-1％、Na 2 O：0.1-0.3％、B 2 O 3 ：1-3％、P 2 O 5 ：1-2％；
The expansion coefficient of the green brick is 2.5-3.5X10 -6 /K(600～20℃)。
Preferably, the chemical composition of the first low-expansion wear-resistant full polished glaze comprises: in mass percent, siO 2 ：40-45％、Al 2 O 3 ：25-30％、CaO：2-4％、MgO：9-10％、K 2 O：0.2-1％、ZnO：1-5％、BaO：3-7％、P 2 O 5 ：2-4％、B 2 O 3 ：1-3％。
Preferably, the initial melting temperature of the first low-expansion wear-resistant full-polished glaze is 1110-1140 ℃, and the thermal expansion coefficient of the first low-expansion wear-resistant full-polished glaze is 3.5-5 multiplied by 10 -6 /K(600～20℃)。
Preferably, the first low-expansion wear-resistant full-polishing glaze is sprayed in a mode of specific gravity of 1.3-1.6, and the glazing quantity of 150-250g/m 2 。
Preferably, the chemical composition of the second low-expansion wear-resistant full-polished glaze comprises: in mass percent, siO 2 ：45-50％、Al 2 O 3 ：20-25％、CaO：2-4％、MgO：7-9％、K 2 O：0.2-1％、Na 2 O：0.2-0.6％、ZnO：5-8％、BaO：6.0-10.0％、P 2 O 5 ：2-4％、B 2 O 3 ：1-3％。
Preferably, the initial melting temperature of the second low-expansion wear-resistant full-polished glaze is 1060-1110 ℃, and the thermal expansion coefficient of the second low-expansion wear-resistant full-polished glaze is 5-5.5X10 -6 /K(600～20℃)。
Preferably, the second low-expansion wear-resistant full-polishing glaze is applied by glaze spraying, the specific gravity is 1.3-1.6, and the glaze spraying amount is 250-350g/m 2 。
Preferably, the highest sintering temperature is 1150-1170 ℃ and the sintering time is 60-80min.
In a second aspect, the invention provides a low-expansion cordierite crystal wear-resistant full-glazed ceramic tile obtained according to the preparation method.
Advantageous effects
According to the invention, the expansion coefficient is reduced by adding cordierite and generating cordierite in situ, and the hardness of the cordierite is high (7.5) and the cordierite has a refractive index similar to that of glass, so that the influence on the transparency of the polished glaze is small, and the transparent full polished glaze has a low expansion coefficient and wear resistance. Meanwhile, the invention solves the problem of poor penetration of the traditional low-expansion ceramic tile by a secondary transparent full glaze spraying mode. The full-polished ceramic tile blank glaze obtained by the preparation method provided by the invention has the advantages of better combination property, low expansion coefficient and better wear resistance and permeability.
Drawings
FIG. 1 is a flow chart of an exemplary low-expansion cordierite crystal wear-resistant full-polished glazed ceramic tile production process;
FIG. 2 (left) is a schematic diagram of the low expansion abrasion resistant glaze indentation of the ceramic tile sample prepared in example 1; FIG. 2 (right) is a schematic drawing of a glazing impression of a conventional glazed ceramic tile;
FIG. 3 is a scanning electron microscope image of the tile surface of the ceramic tile sample prepared in example 1.
Detailed Description
The present invention is further illustrated by the following embodiments, which are to be understood as merely illustrative of the invention and not limiting thereof. Unless otherwise specified, each percentage refers to a mass percent.
The following is an exemplary description of a method for preparing a low-expansion cordierite crystal abrasion-resistant full-glazed ceramic tile, which may include the following steps, in conjunction with fig. 1.
And pressing the green body powder into green bricks. Adding water into the raw materials of the low-expansion ceramic body according to the proportion, mixing, ball milling, sieving, removing iron, spraying, granulating and molding by a press to obtain the low-expansion ceramic body.
In some embodiments, the low expansion ceramic green body is a green bodyThe chemical composition of the material may include: in mass percent, IL:4-6% of SiO 2 ：45-50％、Al 2 O 3 ：25-32％、Fe 2 O 3 ：0.1-0.5％、TiO 2 ：0.1-0.5％、CaO：1-2％、MgO：9-12％、K 2 O：0.5-1％、Na 2 O：0.1-0.3％、B 2 O 3 ：1-3％、P 2 O 5 ：1-2％。
Wherein the initial melting temperature of the low expansion ceramic body can be 1130-1160 ℃; the expansion coefficient of the low expansion ceramic body can be 2.5-3.5X10 -6 /K(600～20℃)。
In some embodiments, the raw material composition of the low expansion ceramic body may include: clay is calculated by mass percent: 30-45% of cordierite clinker powder: 20-45%, calcined talc: 1-10 percent of magnesia clay: 1-5% of boron-magnesium stone: 1-5%, P-containing flux: 1-5%.
The cordierite clinker powder is powder taking cordierite as a main crystal phase. The P-containing flux may be selected from phosphates, preferably calcium phosphates.
And drying the pressed green bricks. The temperature for drying the green bricks can be 150-200 ℃, and the drying time can be 50-90min; controlling the moisture of the dried green bricks to be 0.3-0.5wt%.
And applying overglaze on the surface of the dried green brick. The overglaze is applied on the surface of the dried low-expansion ceramic green body to cover the defects of the green body and promote the color development of the ink-jet pattern.
In some embodiments, the chemical composition of the overglaze may include: in mass percent, IL:4-6% of SiO 2 ：52-55％、Al 2 O 3 ：22-25％、Fe 2 O 3 ：0.2-0.3％、TiO 2 ：0.2-0.3％、CaO：0.3-0.4％、MgO：0.3-0.4％、K 2 O：4-6％、Na 2 O：3-4％、ZrO 2 ：8-14％。
The initial melting temperature of the overglaze can be 1140-1180 ℃, and the expansion coefficient can be 7-8 multiplied by 10 -6 /K(600～20℃)。
In some embodiments, the raw material composition of the overglaze may include: 25-35% of kaolin and zirconium silicate: 20-30%, 15-25% of potassium feldspar and 15-25% of albite.
The overglaze can be applied in a digital glaze spraying mode through two channels, so that the uniformity of the glaze surface can be ensured. Preferably, the gray scale of each channel may be set to 10-15%.
The glazing amount of the overglaze can be 50-100g/m 2 . The digital overglaze has a larger expansion coefficient, the glazing quantity can be precisely controlled by adopting the digital overglaze, and the unstable brick shape caused by unmatched blank glaze can be avoided by adopting a smaller glazing quantity.
And (3) carrying out ink-jet printing on the surface of the green brick after the overglaze is sprayed. The pattern structure of the ink jet printing can be adjusted according to the decorative effect. The green bricks are dried after the pattern is ink-jet printed.
And applying a first low-expansion wear-resistant full-polished glaze on the surface of the green brick after the pattern is printed by the ink jet. The first low-expansion wear-resistant full polished glaze is used as a buffer layer, so that the expansion coefficients of the blank body and the wear-resistant glaze of the outermost layer cannot be excessively different, and the blank body is favorable for maintaining the brick shape.
The chemical composition of the first low-expansion wear-resistant full polished glaze can comprise: in mass percent, siO 2 ：40-45％、Al 2 O 3 ：25-30％、CaO：2-4％、MgO：9-10％、K 2 O：0.2-1％、ZnO：1-5％、BaO：3-7％、P 2 O 5 ：2-4％、B 2 O 3 :1-3%. Preferably, the chemical composition of the first low-expansion wear-resistant full polished glaze can comprise: in mass percent, siO 2 ：40-45％、Al 2 O 3 ：25-30％、Fe 2 O 3 ：0.1-0.5％、TiO 2 ：0.1-0.5％、CaO：2-4％、MgO：9-10％、K 2 O：0.2-1％、ZnO：1-5％、BaO：3-7％、P 2 O 5 ：2-4％、B 2 O 3 :1-3%, loss of burning: 4-6%.
Conventional formulations generally employ P 2 O 5 And the composite material is compounded with potassium-sodium flux, so that the temperature of a green body is reduced, and the formation of cordierite is promoted. Low equivalent state of potassium and sodiumThe metal element has large distance from oxygen ion, small attractive force, small field strength and small single bond energy, and is unfavorable for the improvement of hardness. Because cordierite has poor color development on patterns, the invention uses metal oxides such as BaO, znO and the like, not only can reduce the temperature of a blank, but also is beneficial to color development of ink, meanwhile, the distance between alkaline earth metal and oxygen ions is small, the attraction is large, the field strength is large, the single bond energy is large, the hardness of a glaze layer is beneficial to increase, and the expansion coefficient of a glass phase can be further reduced by introducing B.
The formula of the full polished glaze controls the monovalent alkali metal to be less than 2 percent, and simultaneously, alkaline earth metal with better color development is matched to replace potassium sodium, so that the problem of color development of patterns is solved.
In some embodiments, the initial melting temperature of the first low-expansion wear-resistant full-polished glaze can be 1110-1140 ℃, and the thermal expansion coefficient of the first low-expansion wear-resistant full-polished glaze can be 3.5-5 multiplied by 10 -6 K (600-20 ℃). Due to the expansion coefficient of the ceramic body being 2.5-3.5X10 -6 And (K) (600-20 ℃), the initial melting temperature and the thermal expansion coefficient of the first polished glaze can be controlled within the range so as to better play the role of a buffer layer, avoid the mismatching of the blank glaze, and simultaneously, the early vitrification can be avoided by controlling the melting temperature within the range so as to prevent gas from being discharged.
In some embodiments, the first low-expansion wear-resistant full-polished glaze material composition may include: cordierite Dan Shouliao powder in mass percent: 20-40%, clay: 5-10% of barium carbonate: 5-10% of boron-magnesium stone: 1-5% of calcined talc: 10-15%, zinc oxide: 1-5% of aluminum oxide: 10-20 percent of calcium phosphate: 5-10%, potassium feldspar: 0-5%.
Boron and magnesium are provided by the boron-magnesium source and react with alumina to form cordierite, and the boron is fused into the glass to further reduce the expansion coefficient. Preferably, the molar ratio of magnesium oxide to aluminum oxide in the formulation is controlled to be 1:1, cordierite can be completely reacted and synthesized in this way, and no excessive content is caused, and no increase in expansion coefficient is caused. In addition, the calcium phosphate is used as a strong fluxing agent, is beneficial to synthesis of cordierite and participation of alumina in the reaction (the alumina has higher temperature and low activity).
In some embodiments, the cordierite content in the first low-expansion wear-resistant full polished glaze after firing can be controlled to be 45-55wt% so as to meet the requirement of low expansion coefficient.
The first low-expansion wear-resistant full-polished glaze can be sprayed. Under the condition of lower glazing quantity, the mode of spraying glaze is easier to control.
The specific gravity of the first low-expansion wear-resistant full-polished glaze can be controlled to be 1.3-1.6, and the glazing quantity can be 150-250g/m 2 . The glazing quantity is too low to play a good role of a buffer layer; too high glazing amount can lead to higher cordierite content in the glaze layer, which is unfavorable for the sense of penetration of the blank.
Spraying a second low-expansion wear-resistant full-polished glaze on the surface of the blank body after the first low-expansion wear-resistant full-polished glaze is applied and dried. The influence of the crystal on the penetration of the glaze can be reduced by applying the second low-expansion wear-resistant full polished glaze, namely, the penetration is not influenced while the expansion coefficient and the wear resistance of the glaze layer are ensured.
The chemical composition of the second low-expansion wear-resistant full polished glaze can comprise: in mass percent, siO 2 ：45-50％、Al 2 O 3 ：20-25％、CaO：2-4％、MgO：7-9％、K 2 O：0.2-1％、Na 2 O：0.2-0.6％、ZnO：5-8％、BaO：6.0-10.0％、P 2 O 5 ：2-4％、B 2 O 3 :1-3%. Preferably, the chemical composition of the second low-expansion wear-resistant full polished glaze can comprise: in mass percent, siO 2 ：45-50％、Al 2 O 3 ：20-25％、Fe 2 O 3 ：0.16-0.46％、TiO 2 ：0.10-0.20％、CaO：2-4％、MgO：7-9％、K 2 O：0.2-1％、Na 2 O：0.2-0.6％、ZnO：5-8％、BaO：6.0-10.0％、P 2 O 5 ：2-4％、B 2 O 3 :1-3%, loss of burning: 4.0-6.0%.
Compared with the first low-expansion wear-resistant full-polished glaze, the second low-expansion wear-resistant full-polished glaze properly reduces the content of Mg and Al, thereby properly reducing the synthesis amount of cordierite, simultaneously increasing the content of flux and reducing the melting of the full-polished glazeMelting temperature. In some embodiments, the initial melting temperature of the second low-expansion wear-resistant full-polished glaze can be 1060-1110 ℃, and the thermal expansion coefficient of the second low-expansion wear-resistant full-polished glaze can be 5-5.5X10 -6 K (600-20 ℃). Therefore, the expansion coefficient of the second low-expansion wear-resistant full-polished glaze can be well matched with that of the first low-expansion wear-resistant full-polished glaze, and the melting temperature is lower.
According to the invention, the cordierite content in the second low-expansion wear-resistant full polished glaze is reduced, the expansion coefficient is reduced, the transparency is improved, the melting temperature is reduced, the glass phase content is improved, and finally, the good effect of improving the penetration is achieved.
In some embodiments, the second low-expansion wear-resistant full-polished glaze comprises the following raw materials in percentage by mass: 20-30%, clay: 5-10% of barium carbonate: 10-15% of periclase: 1-5% of calcined talc: 5-10%, zinc oxide: 5-8 percent of aluminum oxide: 15-20%, calcium phosphate: 5-10%, potassium feldspar: 1-5%, albite: 1-5%.
In some embodiments, the cordierite content in the second low-expansion wear-resistant full polished glaze after firing can be controlled to be 35-45% to control the expansion coefficient so as to match the green glaze.
The second low-expansion wear-resistant full-polished glaze can be sprayed; the specific gravity of the second low-expansion wear-resistant full polished glaze can be controlled to be 1.3-1.6, and the glazing quantity can be 250-350g/m 2 . The too low specific gravity can cause the phenomenon of glaze flowing when the moisture of the glaze is too high; too high specific gravity can lead to too high solid content of the glaze and uneven glaze surface. The overhigh glazing amount can lead to air bubbles not being easy to be discharged and air holes on the glaze; too little glazing amount can cause polishing through the exposed bottom after polishing.
And (5) drying and sintering. And drying the second low-expansion wear-resistant full-polished green body sprayed with the low-expansion wear-resistant full-polished ceramic tile, and then firing the green body in a kiln to obtain the low-expansion cordierite crystal wear-resistant full-polished ceramic tile.
In some embodiments, the maximum firing temperature may be 1150-1170 ℃ and the firing time may be 60-80min. The sintering temperature is too low, so that the water absorption rate of the green body is higher, and the green body is easy to deform; too high firing temperatures can result in the glaze being prone to bubbles and pinholes.
Polishing, packaging and warehousing. The polishing mesh number can be 240 mesh 10 groups, 320 mesh 10 groups, 400 mesh 10 groups, 600 mesh 5 groups, 800 mesh 5 groups, 1000 mesh 4 groups, 1500 mesh 4 groups, 2000 mesh 4 groups, 3000 mesh 8 groups for the arrangement of the abrasive blocks.
In the formula design of the low-expansion wear-resistant transparent full polished glaze, the expansion coefficient is reduced in a mode of externally adding cordierite and generating cordierite in situ. Moreover, because the cordierite has high hardness (7.5) and similar refractive index to glass, the transparent full-polished glaze has smaller influence on the transparency of the polished glaze, and has lower expansion coefficient and wear resistance. Meanwhile, the invention solves the problem of poor penetration of the traditional low-expansion ceramic tile by a secondary transparent full glaze spraying mode. The full-polished ceramic tile blank glaze obtained by the preparation method provided by the invention has the advantages of better combination property, low expansion coefficient and better wear resistance and permeability.
The low-expansion cordierite crystal wear-resistant full-polished glazed ceramic tile prepared by the preparation method provided by the invention comprises the following steps from bottom to top: the low-expansion wear-resistant full-polishing glaze comprises a blank layer, a surface glaze layer, a pattern layer, a first low-expansion wear-resistant full-polishing glaze layer and a second low-expansion wear-resistant full-polishing glaze layer; wherein the content of cordierite in the first low-expansion wear-resistant full-polished glaze layer is 45-55wt%, and the content of cordierite in the second low-expansion wear-resistant full-polished glaze layer is 35-45%.
The low-expansion cordierite crystal wear-resistant full-polished glazed ceramic tile obtained by the preparation method provided by the invention has the thermal stability reaching 20-250 ℃ through the detection of CJ/T157-2017 'the household gas cooker application layer toughened glass panel'. According to GB/T3810.7-2016 ceramic tile test method part 7: measurement of abrasion resistance of glazed brick surface the abrasion resistance of the sample was measured, and the test results were as follows: the abrasion resistance was grade 4.
The present invention will be further illustrated by the following examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
Example 1
(1) And pressing the green body powder into green bricks. Wherein the chemical composition of the low-expansion ceramic green body raw material comprises: in mass percent, IL:6%, siO 2 ：47％、Al 2 O 3 ：28％、Fe 2 O 3 ：0.5％、TiO 2 ：0.2％、CaO：2％、MgO：11％、K 2 O：0.6％、Na 2 O：0.2％、B 2 O 3 ：3％、P 2 O 5 :1.5%; expansion coefficient of 2.5X10 -6 /K(600～20℃)。
(2) And drying the pressed green bricks. Controlling the moisture of the dried green bricks to be 0.3-0.5wt%.
(3) And applying overglaze on the surface of the dried green brick. The chemical composition of the overglaze comprises the following components in percentage by mass: 5% of SiO 2 ：53％、Al 2 O 3 ：22％、Fe 2 O 3 ：0.2％、TiO 2 ：0.2％、CaO：0.3％、MgO：0.3％、K 2 O：5％、Na 2 O：4％、ZrO 2 :10%; expansion coefficient of 7-8×10 -6 K (600-20 ℃); the overglaze is applied in a digital glaze spraying mode through two channels, and the gray scales of the two channels are respectively set to 15 percent and 15 percent; glazing amount was 70g/m 2 。
(4) And (5) carrying out ink-jet printing on the surface of the green brick after the overglaze is sprayed, and drying.
(5) And applying a first low-expansion wear-resistant full-polished glaze on the surface of the green brick after the pattern is printed by the ink jet. The chemical composition of the first low-expansion wear-resistant full polished glaze comprises: siO in mass percent 2 ：42％、Al 2 O 3 ：27％、Fe 2 O 3 ：0.2％、TiO 2 ：0.3％、CaO：2％、MgO：10％、K 2 O：0.5％、ZnO：3％、BaO：5％、P 2 O 5 ：2％、B 2 O 3 :3%, loss on burning: 5%; the initial melting temperature is 1120 ℃, and the thermal expansion coefficient is 3.5 multiplied by 10 -6 K (600-20 ℃); the first low-expansion wear-resistant full-polished glaze comprises the following raw materials: the cordierite cooked powder comprises 30 mass percent of clay: 10 percent of barium carbonate: 10 percent of kieserite: 5%, calcined talc: 15%, zinc oxide: 5% of aluminum oxide: 13%, calcium phosphate: 7%, potassium feldspar: 5%; the application mode is spraying glaze, the specific gravity is 1.4, and the glazing glaze amount is 180g/m 2 。
(6) Spraying a second low-expansion wear-resistant full-polished glaze on the surface of the blank body after the first low-expansion wear-resistant full-polished glaze is applied and dried. The chemical composition of the second low-expansion wear-resistant full polished glaze comprises, by mass percentage, siO 2 ：45％、Al 2 O 3 ：21％、Fe 2 O 3 ：0.3％、TiO 2 ：0.2％、CaO：3％、MgO：8％、K 2 O：0.2％、Na 2 O：0.3％、ZnO：6％、BaO：8％、P 2 O 5 ：3％、B 2 O 3 :1%, loss on burning: 4%; the initial melting temperature is 1100 ℃, and the thermal expansion coefficient is 5 multiplied by 10 -6 K (600-20 ℃); the second low-expansion wear-resistant full-polished glaze comprises the following raw materials: cordierite Dan Shouliao powder in mass percent: 30%, clay: 10 percent of barium carbonate: 15% of periclase: 3%, calcined talc: 7%, zinc oxide: 8%, alumina: 15%, calcium phosphate: 7%, potassium feldspar: 2%, albite: 3%; the application mode is spraying glaze, the specific gravity is 1.4, and the glazing amount is 300g/m 2 。
(7) Drying and sintering. And (3) spraying the second low-expansion wear-resistant full-polished glaze and sintering the dried green body to obtain the low-expansion cordierite crystal wear-resistant full-polished glazed ceramic tile. The highest firing temperature is 1160 ℃ and the firing time is 80min.
(8) Polishing, packaging and warehousing.
FIG. 2 (left) is a schematic diagram of the low expansion abrasion resistant glaze indentation of the ceramic tile sample prepared in example 1; fig. 2 (right) is a schematic diagram of glazing impression of a common glazed ceramic tile. It can be seen from the figure that the common polished glaze has larger indentation size and obvious crack growth at four corners of the indentation, while the abrasion-resistant glaze sample has small indentation size and no obvious crack growth can be observed.
FIG. 3 is a scanning electron microscope image of the tile surface of the ceramic tile sample prepared in example 1. As can be seen from the figure, the glaze has more irregular crystal particles and is more densely distributed on the surface of the glaze, so that the wear resistance is improved.
Comparative example 1
The preparation process is described in reference to example 1, with the main differences: the second low-expansion wear-resistant full-polishing glaze is firstly applied, and then the first low-expansion wear-resistant full-polishing glaze is applied.
Because the first low-expansion wear-resistant full-polished glaze is lack between the green body and the second low-expansion wear-resistant full-polished glaze as an intermediate layer buffer, the sintered green body is uneven; meanwhile, the initial melting temperature of the second low-expansion wear-resistant full-polishing glaze is lower than that of the first low-expansion wear-resistant full-polishing glaze, and when the second low-expansion wear-resistant full-polishing glaze is placed at the position of the middle layer, gas of the green body is prevented from being discharged.
Comparative example 2
The preparation process is described in reference to example 1, with the main differences: only the first low-expansion wear-resistant full-polished glaze is applied, and the second low-expansion wear-resistant full-polished glaze is not applied.
The ceramic sample prepared in the comparative example has a very thin full glaze polishing layer and is easy to polish through.
Comparative example 3
The preparation process is described in reference to example 1, with the main differences: only the second low-expansion wear-resistant full-polished glaze is applied, and the first low-expansion wear-resistant full-polished glaze is not applied.
In the ceramic sample prepared in the comparative example, the difference between the expansion coefficients of the green body and the full polished glaze is too large, so that the brick type upwarps.
Claims (10)
1. The preparation method of the low-expansion cordierite crystal wear-resistant full-polished glazed ceramic tile is characterized by comprising the following steps of:
applying surface glaze on the surface of the green brick;
printing patterns on the surface of the green bricks after the overglaze is applied in an inkjet mode;
applying a first low-expansion wear-resistant full-polished glaze on the surface of the green brick after the pattern is printed by ink jet;
applying a second low-expansion wear-resistant full-polishing glaze on the surface of the blank body to which the first low-expansion wear-resistant full-polishing glaze is applied;
and firing to obtain the low-expansion cordierite crystal wear-resistant full-polished glazed ceramic tile.
2. The method of claim 1, wherein the green brick raw material comprises the following chemical composition: in mass percent, IL:4-6% of SiO 2 ：45-50％、Al 2 O 3 ：25-32％、Fe 2 O 3 ：0.1-0.5％、TiO 2 ：0.1-0.5％、CaO：1-2％、MgO：9-12％、K 2 O：0.5-1％、Na 2 O：0.1-0.3％、B 2 O 3 ：1-3％、P 2 O 5 ：1-2％；
The expansion coefficient of the green brick is 2.5-3.5X10 -6 /K(600～20℃)。
3. The method according to claim 1 or 2, wherein the chemical composition of the first low-expansion wear-resistant full polished glaze comprises: in mass percent, siO 2 ：40-45％、Al 2 O 3 ：25-30％、CaO：2-4％、MgO：9-10％、K 2 O：0.2-1％、ZnO：1-5％、BaO：3-7％、P 2 O 5 ：2-4％、B 2 O 3 ：1-3％。
4. The method according to any one of claims 1 to 3, wherein the initial melting temperature of the first low-expansion wear-resistant full-polished glaze is 1110 to 1140 ℃, and the thermal expansion coefficient of the first low-expansion wear-resistant full-polished glaze is 3.5 to 5 x 10 -6 /K(600～20℃)。
5. The method according to any one of claims 1 to 4, wherein the first low-expansion wear-resistant full-polishing glaze is applied by spraying glaze, the specific gravity is 1.3 to 1.6, and the glazing amount is 150 to 250g/m 2 。
6. The method of any one of claims 1-5, wherein the second low-expansion wear-resistant full-polished glaze comprises the chemical composition of: in mass percent, siO 2 ：45-50％、Al 2 O 3 ：20-25％、CaO：2-4％、MgO：7-9％、K 2 O：0.2-1％、Na 2 O：0.2-0.6％、ZnO：5-8％、BaO：6.0-10.0％、P 2 O 5 ：2-4％、B 2 O 3 ：1-3％。
7. The method according to any one of claims 1 to 6, wherein the initial melting temperature of the second low-expansion wear-resistant full-polished glaze is 1060 to 1110 ℃, and the thermal expansion coefficient of the second low-expansion wear-resistant full-polished glaze is 5 to 5.5x10 -6 /K(600～20℃)。
8. The method according to any one of claims 1 to 7, wherein the second low-expansion wear-resistant full-polishing glaze is applied by spraying glaze, the specific gravity is 1.3 to 1.6, and the glazing amount is 250 to 350g/m 2 。
9. The method according to any one of claims 1 to 8, wherein the maximum firing temperature is 1150 to 1170 ℃ and the firing time is 60 to 80min.
10. A low-expansion cordierite crystal abrasion-resistant full-glazed ceramic tile obtained according to the preparation method of any one of claims 1 to 9.
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