CN116282922B - Nano matte super-wear-resistant diamond glaze, ceramic tile and preparation method thereof - Google Patents
Nano matte super-wear-resistant diamond glaze, ceramic tile and preparation method thereof Download PDFInfo
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- CN116282922B CN116282922B CN202310577497.2A CN202310577497A CN116282922B CN 116282922 B CN116282922 B CN 116282922B CN 202310577497 A CN202310577497 A CN 202310577497A CN 116282922 B CN116282922 B CN 116282922B
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- 239000010432 diamond Substances 0.000 title claims abstract description 96
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 96
- 239000000919 ceramic Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 66
- 229910052878 cordierite Inorganic materials 0.000 claims abstract description 61
- 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 claims abstract description 61
- 239000000843 powder Substances 0.000 claims abstract description 49
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000010434 nepheline Substances 0.000 claims abstract description 28
- 229910052664 nepheline Inorganic materials 0.000 claims abstract description 28
- 239000010435 syenite Substances 0.000 claims abstract description 22
- 239000011787 zinc oxide Substances 0.000 claims abstract description 22
- 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 claims abstract description 21
- 229910052637 diopside Inorganic materials 0.000 claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 15
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 15
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000011161 development Methods 0.000 claims abstract description 11
- 239000006004 Quartz sand Substances 0.000 claims abstract description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 34
- 239000000126 substance Substances 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 17
- 238000010304 firing Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 238000005245 sintering Methods 0.000 claims description 16
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 238000010791 quenching Methods 0.000 claims description 6
- 230000000171 quenching effect Effects 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 239000011435 rock Substances 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 26
- 230000000694 effects Effects 0.000 abstract description 13
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract description 3
- 239000003607 modifier Substances 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 23
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 16
- 230000006872 improvement Effects 0.000 description 10
- 238000005507 spraying Methods 0.000 description 10
- 239000011449 brick Substances 0.000 description 9
- 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 9
- 229910052863 mullite Inorganic materials 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 238000013461 design Methods 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 6
- 238000007641 inkjet printing Methods 0.000 description 6
- 239000000454 talc Substances 0.000 description 6
- 229910052623 talc Inorganic materials 0.000 description 6
- 235000012222 talc Nutrition 0.000 description 6
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 6
- 239000010433 feldspar Substances 0.000 description 5
- 238000009825 accumulation Methods 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 239000013081 microcrystal Substances 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 229910052661 anorthite Inorganic materials 0.000 description 3
- 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 3
- 239000010459 dolomite Substances 0.000 description 3
- 229910000514 dolomite Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- -1 microclinite Inorganic materials 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910052845 zircon Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052656 albite Inorganic materials 0.000 description 1
- 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 1
- 239000005328 architectural glass Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical group [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229910052652 orthoclase Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
Abstract
The invention belongs to the technical field of building ceramics, and particularly discloses a nano matte super-wear-resistant diamond glaze, a ceramic tile and a preparation method thereof, wherein the nano matte super-wear-resistant diamond glaze comprises the following raw materials in parts by weight: 10-15 parts of kaolin; 3-6 parts of quartz sand; 10-20 parts of diopside; 20-30 parts of basalt; 5-10 parts of aluminum oxide; 3-6 parts of cordierite; 15-20 parts of cordierite type matte frit powder; 10-15 parts of a color-developing regulator; the color-developing modifier includes nepheline syenite and calcined zinc oxide. According to the invention, through optimizing and reasonably compounding the raw materials, the silicon-aluminum ratio of the glaze is controlled in a proper range, the nano matte super wear-resistant diamond glaze with excellent comprehensive performance is prepared, when the nano matte super wear-resistant diamond glaze is applied to ceramic tiles, the Mohs hardness of the glaze can be more than 7, the wear resistance can reach 5, the visible light transmittance of the glaze layer can reach 68-72%, and the nano matte super wear-resistant diamond glaze has a good color development effect.
Description
Technical Field
The invention belongs to the technical field of building ceramics, and particularly relates to a nano matte super-wear-resistant diamond glaze, a nano matte super-wear-resistant ceramic tile and a preparation method of the nano matte super-wear-resistant diamond glaze and the nano-wear-resistant ceramic tile.
Background
The decoration effect of the ceramic is mainly realized by glaze, the matte glaze is a ceramic glaze with the glossiness between that of gloss and matt, the glossiness is about 10 degrees, the glaze surface is fine and smooth and moist, no strong reflection exists, and a soft, quiet and comfortable visual feeling is provided for people. The peculiar frosted feeling of the matte surface eases diffuse reflection formed by illumination, is not dizziness and dazzling, is good for eyes, and is favored by consumers. The diamond glaze is named because the glaze surface has the high hardness and high wear resistance of diamond.
At present, diamond glaze mainly separates out crystals with high hardness in glaze melt or directly adds high-hardness raw materials such as zirconia, zircon sand, zirconium-containing silicate and the like to improve the wear resistance of products, but most of the raw materials are opacifying brighteners, and a large amount of the raw materials are introduced to reduce the light transmittance of a glaze layer, influence the color development of the glaze surface and have higher glossiness. Meanwhile, matte and light transmittance are a pair of contradictory properties, and in general, the lower the glossiness (matte), the worse the light transmittance.
The existing ceramic glaze cannot have matte, high hardness, high wear resistance and high light transmittance.
For example, chinese patent publication No. CN 113896421 discloses a wear-resistant digital ceramic glaze, which comprises 50-60 parts by mass of frit, 10-20 parts by mass of kaolin, 10-15 parts by mass of zirconium silicate, 1-3 parts by mass of zirconium oxide, 0-20 parts by mass of zircon and 1-3 parts by mass of barium sulfate as main components, and by adding zirconium silicate with different particle diameters and combining with zirconium oxide, the wear resistance of the glaze is improved. A large amount of zirconium opacifying raw materials are used in the formula of the glaze, the gloss of the glaze is difficult to realize matte, and the light transmittance is reduced. The Chinese patent with publication number of CN106946460A discloses a high wear-resistant polished glaze material, which consists of raw glaze powder and frit powder, wherein: the raw glaze powder comprises kaolin, calcined kaolin, quartz, dolomite, wollastonite, calcined talcum, nepheline, zinc oxide and strontium carbonate, and the wear resistance of the glaze is improved through cordierite, anorthite and nepheline in the raw glaze powder, but the wear resistance of the prepared glaze can only reach 4-grade 6000 revolutions and cannot reach the higher requirement of diamond glaze.
Therefore, there is a need to develop a ceramic glaze, which can realize matte, high hardness, high wear resistance, and good light transmittance without affecting the color development effect of the product on the premise of ensuring the quality of the glaze.
Disclosure of Invention
The invention provides a nano matte super-wear-resistant diamond glaze, a ceramic tile and a preparation method thereof, which are used for solving one or more technical problems in the prior art and at least providing a beneficial selection or creation condition.
In order to solve the technical problems, the first aspect of the invention provides a nano matte super wear-resistant diamond glaze, which comprises the following raw materials in parts by weight:
10-15 parts of kaolin;
3-6 parts of quartz sand;
10-20 parts of diopside;
20-30 parts of basalt;
5-10 parts of aluminum oxide;
3-6 parts of cordierite;
15-20 parts of cordierite type matte frit powder;
10-15 parts of a color-developing regulator;
the color-developing modifier includes nepheline syenite and calcined zinc oxide.
The semi-frit matte glaze compounded by the raw materials and the frit has wider application range compared with the full-frit matte glaze, and can be tailored according to each kiln, so that the semi-frit matte glaze is suitable for the temperature system of the kiln and is matched with the performances of a blank body and the base glaze, and the stability of a product is improved. According to the invention, through optimizing and reasonably compounding the raw materials, the silicon-aluminum ratio of the glaze is controlled in a proper range, so that the nano matte super-wear-resistant diamond glaze is prepared, and on the premise of ensuring the quality of matte and glaze, the high hardness, high wear resistance, good light transmittance and good color development effect are realized.
Specifically, the frit disclosed by the invention is a cordierite type matte frit, so that a large number of cordierite crystallites are formed by the fired glaze layer in a chromatography mode, the hardness of the glaze layer is improved, and the wear resistance of the glaze layer is improved. The main raw material components of the raw glaze are diopside and basalt, and the diopside and the basalt form cordierite microcrystals with alumina and kaolin in the sintering process. Adding a small amount of cordierite as high Wen Jinghe, and initiating new crystal development, so that diopside and basalt react with clay at high temperature to form cordierite; in addition, raw materials and cordierite matte frit powder are used for precipitating cordierite crystals in the sintering process, and because atoms on a crystal boundary are disordered in arrangement, a plurality of defects such as vacancies, dislocation and bond deformation exist, so that the crystal boundary is in a stress distortion state, the energy level on the crystal boundary is higher, and the crystal boundary becomes a region which is nucleated preferentially in solid phase transition, so that the cordierite crystals formed in the cooling process of the glaze take the added cordierite as a crystallization carrier, and a large amount of precipitation of the cordierite crystals is promoted. Meanwhile, diopside and basalt react with alumina and kaolin in situ in the sintering process to generate mullite crystals, so that on one hand, the mullite crystals can act together with cordierite crystals to further improve the hardness of the glaze layer, and on the other hand, the mullite crystals are beneficial to improving the light transmittance of the glaze layer.
Meanwhile, in order to prevent excessive growth of crystals and decrease of light transmittance of a glaze layer, a certain amount of quartz sand is added into raw glaze, and the quartz sand can be partially melted into a glaze melt at high temperature to increase viscosity of the melt, so that growth of the crystals is controlled, cordierite and mullite crystals are separated out in a microcrystalline form, and devitrification of the glaze layer caused by growth of the crystals is prevented; and the unmelted quartz particles are used as a framework, so that the hardness, wear resistance and light transmittance of the glaze layer are further improved.
In addition, the glaze of the invention is added with a certain amount of chromophoric regulator nepheline syenite and calcined zinc oxide, wherein: the main mineral composition of the nepheline syenite is a solid solution of orthoclase, microclinite, albite and nepheline, which is not only beneficial to increasing the expansion coefficient of the glaze and enabling low-expansion cordierite in the glaze to be better adapted to the ground glaze and the green body layer, but also has good promoting effect on the light transmittance of the glaze, so as to be beneficial to improving the color development effect of the glaze. The calcined zinc oxide is the zinc oxide calcined at the high temperature of 1250-1280 ℃, and has the functions of improving the glaze property of the glaze and improving the color development performance of the glaze.
Preferably, in the chemical composition of the nano matte super wear-resistant diamond glaze, siO 2 With Al 2 O 3 The molar ratio of (3.5-4.5): 1. the glossiness of the glaze is regulated to be about 10 by controlling the silicon-aluminum ratio in the glaze component, so that the matte is realized.
As a further improvement of the above-mentioned scheme, the chemical composition of the cordierite-type matt frit powder comprises, in weight percent: siO (SiO) 2 40-50%，Al 2 O 3 20-30%，K 2 O 2-3%，Na 2 1-2% of O, 3-4% of CaO, 15-20% of MgO and 2-4% of ZnO. The invention lays a foundation for the precipitation of cordierite crystals by adjusting the chemical composition of the frit to enable the frit to fall in a cordierite crystallization area.
As a further improvement of the scheme, in the chemical composition of the cordierite-type matte frit powder, siO 2 With Al 2 O 3 The molar ratio of (3-4): 1, siO in the nano matte super wear-resistant diamond glaze 2 With Al 2 O 3 Is beneficial to promoting the precipitation of cordierite, mullite and other crystals in the diamond glaze, thereby realizing the matte effect of the glaze layer.
Preferably, in the chemical composition of the cordierite type matte frit powder, siO 2 With Al 2 O 3 The molar ratio of (3.1-3.4): 1.
as a further improvement of the above scheme, the mass ratio of the nepheline syenite to the calcined zinc oxide is (0.5-1.2): 1. the comprehensive performance of the glaze is regulated by controlling the dosage relation of nepheline syenite and calcined zinc oxide, so that the glaze has wider application range and the light transmittance and the color development performance of the glaze are improved.
Preferably, the chemical composition of the basalt comprises the following components in percentage by weight: siO (SiO) 2 44-48%，Al 2 O 3 12-14%，K 2 O 1-3%，Na 2 O 2-4%，CaO14-18%，MgO12-16%，P 2 O 5 0.8-1.4%，Fe 2 O 3 0.2-0.4%，FeO 0.3-0.6%，MnO 0.2-0.4%，TiO 2 1-4%. Basalt itself has higher hardness and wear resistance, and the main component is SiO 2 、Al 2 O 3、 CaO and MgO, when sintered at high temperature, are synthesized into cordierite, mullite and anorthite together with kaolin and alumina, so that the mechanical properties of the glaze layer are improved together.
Preferably, the chemical composition of the diopside comprises the following components in percentage by weight: siO (SiO) 2 52-55%，Al 2 O 3 1-2%，K 2 O 0.7-0.9%，Na 2 O 0.1-0.2%，CaO 21-24%，MgO 20-22%，Fe 2 O 3 0.4-0.6%, feO 0.4-0.6%. Diopside is calcium magnesium metasilicate with a structural formula of CaMg [ Si ] 2 O 6 ]The ceramic material can be used as a high-temperature flux, and can be used for synthesizing cordierite and anorthite together with kaolin and alumina during high-temperature sintering so as to improve the mechanical property of a glaze layer.
Preferably, the chemical composition of the nepheline syenite comprises, in weight percent: siO (SiO) 2 55-60%，Al 2 O 3 20-25%，K 2 O 5-10%，Na 2 O 8-10%，CaO 0.8-1.0%，MgO 0.1-0.4%，Fe 2 O 3 0.8-1.1%，TiO 2 0.3-0.5%. The nepheline syenite has good fluxing property, has better thermal stability and mechanical strength compared with the common feldspar and nepheline, and is more beneficial to the light transmittance of the glaze.
The second aspect of the invention provides a preparation method of the nano matte super wear-resistant diamond glaze, which is used for preparing the nano matte super wear-resistant diamond glaze of the first aspect of the invention, and comprises the following steps:
(1) Mixing raw materials for preparing cordierite type matte frit powder, pouring the mixture into water for quenching after melting, wherein the melting temperature is 1450-1500 ℃, and the melting time is 8-10 hours, so as to obtain frit particles; then crushing the frit particles to obtain cordierite type matte frit powder;
(2) Mixing the cordierite-type matt frit powder with other raw materials for preparing the nano matt super-wear-resistant diamond glaze, and performing wet ball milling to obtain the nano matt super-wear-resistant diamond glaze.
As a further improvement of the above proposal, the particle size of the cordierite-type matt frit powder is 100-120 mesh. If the particle size of the frit powder is too small, agglomeration is easy to occur, so that the glaze is unevenly mixed; the particle size of the frit powder is too large, and the wet ball milling time is increased due to the higher hardness of the frit.
As a further improvement of the scheme, the fineness of the nano matte super wear-resistant diamond glaze is 0.3-0.5wt% of 325 mesh screen residue.
The third aspect of the invention provides a nano matte super wear-resistant ceramic tile, which comprises a blank body and a diamond glaze layer arranged on the upper surface of the blank body, wherein the diamond glaze layer is formed by firing the nano matte super wear-resistant diamond glaze of the first aspect of the invention.
As a further improvement of the above scheme, the upper surface of the blank is provided with a plurality of protrusions and a plurality of grooves, all the protrusions are respectively arranged along the transverse direction and the longitudinal direction of the blank, all the grooves are respectively arranged along the transverse direction and the longitudinal direction of the blank, and the grooves are arranged between any two adjacent protrusions in the transverse direction and the longitudinal direction of the blank.
Specifically, the convex parts on the green body can increase the surface friction coefficient of the nano matte super wear-resistant ceramic tile; when the convex parts on the green body are excessively worn, the grooves on the green body can still ensure that the nano matte super wear-resistant ceramic bricks have high surface friction coefficients, so that the nano matte super wear-resistant ceramic bricks have double anti-skid functions. Moreover, a plurality of convex parts and a plurality of grooves are all arranged in an array, so that the nano matte super wear-resistant ceramic tile can play an excellent anti-slip effect in a plurality of directions, and the blank body with the structure is matched with the diamond glaze layer made of the nano matte super wear-resistant diamond glaze, so that the anti-slip wear resistance of the nano matte super wear-resistant ceramic tile can be greatly enhanced, the convex parts on the ceramic tile are not easy to wear, and the service life of the nano matte super wear-resistant ceramic tile is prolonged. And when the nano matte super wear-resistant ceramic tile has water accumulation, the water accumulation can flow to the groove on the blank body, so that the problem of slipping easily is avoided.
As a further improvement of the scheme, the thickness of the diamond glaze layer is 0.05-0.15mm. As the diamond layer contains a large number of microcrystals, the light transmittance of the diamond layer is improved by controlling the thickness of the glaze layer.
As a further improvement of the scheme, a ground coat layer and an ink-jet printing pattern layer are sequentially arranged between the green body and the diamond glaze layer from bottom to top.
Preferably, the raw material components of the primer layer comprise the following components in parts by weight: 8-12 parts of air knife soil, 5-8 parts of calcined soil, 12-18 parts of quartz powder, 12-18 parts of calcined alumina, 2-4 parts of talcum, 30-40 parts of feldspar, 10-15 parts of nepheline and 5-10 parts of zirconium silicate. The expansion coefficient of the ground coat layer is similar to that of the diamond coat layer, and the adaptability is good.
The invention has no special requirements on the green body, and the green body of the common ceramic brick is adopted.
The fourth aspect of the invention provides a preparation method of a nano matte super wear-resistant ceramic tile, which is used for preparing the nano matte super wear-resistant ceramic tile according to the third aspect of the invention, and comprises the following steps:
(1) According to the preparation method of the nano matte super wear-resistant diamond glaze, the diamond glaze is prepared;
(2) And applying the diamond glaze on the green body to form a diamond glaze layer, and drying and sintering to obtain the nano matte super wear-resistant ceramic tile.
As a further improvement of the above scheme, the firing temperature schedule is: firstly, raising the temperature to 950-1000 ℃ at the temperature raising rate of 15-18 ℃/min, and preserving the heat for 10-15min; then the temperature is increased to the highest firing temperature at the heating rate of 8-10 ℃/min, the temperature is kept for 8-10min, and finally the kiln is taken out for cooling; the highest sintering temperature is 1150-1200 ℃.
Specifically, the temperature is raised to about 950-1000 ℃ at a relatively fast heating rate, at this time, mullite and cordierite crystals start to nucleate and grow successively, and heat preservation is carried out for a certain time, so that the crystals are fully nucleated; then the heating rate is slowed down to continuously heat up to the highest firing temperature, at this time, mullite and cordierite crystals nucleate and grow, so as to prevent the crystals from growing greatly, and the crystals exist in the glaze layer in the form of nano-scale microcrystals, and the heat preservation time is not suitable to be overlong. By controlling the firing system, a large amount of cordierite and mullite microcrystals are precipitated in the glaze layer, so that the hardness and wear resistance of the glaze layer are improved, and the light transmission and color development effects are not reduced.
As a further improvement of the scheme, the preparation method of the nano matte super wear-resistant ceramic tile comprises the following steps:
(1) The diamond glaze is prepared by adopting the preparation method of the nano matte super wear-resistant diamond glaze of the second aspect of the invention;
(2) The base glaze is firstly applied on the green body, then the decoration pattern is printed by ink jet, and then the diamond glaze is applied to form a base glaze layer, an ink jet printing pattern layer and a diamond glaze layer respectively, and the nano matte super wear-resistant ceramic tile is obtained after drying and sintering.
Compared with the prior art, the technical scheme of the invention has at least the following technical effects or advantages:
the invention adopts semi-frit matte glaze, takes cordierite matte frit powder, basalt and diopside as main raw materials, fully exerts the effective chemical composition of each raw material, utilizes the characteristics of each raw material and the interaction among the raw materials, and simultaneously is matched with a certain amount of ceramic basic raw materials of kaolin, quartz sand and alumina; the color-developing regulator comprises nepheline syenite and calcined zinc oxide, a small amount of cordierite is added as a crystal nucleus forming agent, and through optimizing and reasonably compounding all raw materials, the silicon-aluminum ratio of the glaze is controlled within a proper range, the nano matte super wear-resistant diamond glaze with excellent comprehensive performance is prepared, when the nano matte super wear-resistant diamond glaze is applied to ceramic tiles, the Mohs hardness of the glaze surface is more than 7, the wear resistance can reach 5, the visible light transmittance of the glaze layer reaches 68-72%, and the nano matte super wear-resistant diamond glaze has good color-developing effect.
Drawings
FIG. 1 is a top view of a part of a structure cut out from a blank provided by an embodiment of the present invention;
FIG. 2 is a schematic cross-sectional view of section A-A of FIG. 1;
FIG. 3 is a top view of a portion of a blank according to another embodiment of the present invention;
wherein, the reference numerals are as follows: 100. a blank body; 200. a convex portion; 300. a groove; 400. drainage groove.
Detailed Description
The present invention is described in detail below with reference to examples to facilitate understanding of the present invention by those skilled in the art. It is specifically pointed out that the examples are given solely for the purpose of illustration of the invention and are not to be construed as limiting the scope of the invention, since numerous insubstantial modifications and variations of the invention will be within the scope of the invention, as described above, will become apparent to those skilled in the art. Meanwhile, the raw materials mentioned below are not specified, and are all commercial products; the process steps or preparation methods not mentioned in detail are those known to the person skilled in the art.
The green body used in the examples and the comparative examples of the present invention comprises the following raw materials in parts by weight: 35 parts of stone powder, 30 parts of medium-temperature sand, 10 parts of high-temperature sand, 3 parts of talcum and 25 parts of clay.
The base glaze layer comprises the following raw material components in parts by weight: 10 parts of air knife soil, 7 parts of calcined soil, 15 parts of quartz powder, 15 parts of calcined alumina, 3 parts of talcum, 35 parts of feldspar, 15 parts of nepheline and 6 parts of zirconium silicate.
Example 1
The nano matt super wear-resistant diamond glaze comprises the following raw material components in parts by weight:
10 parts of kaolin;
3 parts of quartz sand;
10 parts of diopside;
25 parts of basalt;
8 parts of aluminum oxide;
4 parts of cordierite;
20 parts of cordierite type matte frit powder;
6 parts of nepheline syenite;
7 parts of calcined zinc oxide.
Wherein: the chemical composition of the cordierite type matte frit powder comprises the following components in percentage by weight: siO (SiO) 2 46.5%，Al 2 O 3 25.5%，K 2 O2.3%，Na 2 O1.7%, caO 3.3%, mgO 17.7% and ZnO 3.0%. SiO in chemical composition of cordierite type matte frit powder 2 With Al 2 O 3 The molar ratio of (3) is 3.1:1.
the basalt comprises the following chemical components in parts by weight: siO (SiO) 2 46.5%，Al 2 O 3 13.8%，K 2 O 2.2%，Na 2 O 2.6%，CaO 14.6%，MgO 15.1%，P 2 O 5 1.2%，Fe 2 O 3 0.3%，FeO 0.4%，MnO 0.3%，TiO 2 3.0%。
The diopside comprises the following chemical compositions in parts by weight: siO (SiO) 2 54.1%，Al 2 O 3 1.5%，K 2 O 0.8%，Na 2 O 0.1%，CaO 22.3%，MgO 20.2%，Fe 2 O 3 0.5%，FeO 0.5%。
The chemical composition of nepheline syenite comprises the following components in parts by weight: siO (SiO) 2 57.8%，Al 2 O 3 23.9%，K 2 O 6.5%，Na 2 O 9.3%，CaO 0.9%，MgO 0.2%，Fe 2 O 3 1.0%，TiO 2 0.4%。
The preparation method of the nano matte super wear-resistant ceramic tile comprises the following steps:
(1) Mixing raw materials for preparing cordierite matte frit powder according to a raw material ratio, melting for 9 hours at 1500 ℃, pouring into water, quenching to obtain frit particles; then crushing the frit particles to obtain cordierite type matte frit powder with fineness of 100 meshes;
(2) Mixing the cordierite-type matte frit powder prepared in the step (1) with other raw materials according to the proportion of the raw materials, adding water for ball milling (the mass ratio of the raw materials to the water is 100:40), and obtaining the nano matte super wear-resistant diamond glaze with the fineness of 325 meshes and 0.4 weight percent of screen residue;
(3) Mixing the raw materials of the ground glaze layer according to a proportion, adding water for ball milling (the mass ratio of the raw materials to the water is 100:40), and obtaining the ground glaze with the fineness of 325 meshes and 0.4 weight percent of screen residue;
(4) Spraying the base glaze prepared in the step (3) on the green body, printing a decorative pattern by ink jet, spraying the nano matte super-wear-resistant diamond glaze prepared in the step (2) to form a base glaze layer, an ink jet printing pattern layer and a diamond glaze layer, and drying and sintering to obtain the nano matte super-wear-resistant ceramic tile of the embodiment, wherein the thickness of the diamond glaze layer is 0.1mm.
The firing temperature system is as follows: firstly, heating to 980 ℃ at a heating rate of 16 ℃/min, and preserving heat for 12min; then the temperature is raised to 1160 ℃ at the heating rate of 8 ℃/min, the heat is preserved for 10min, and finally the kiln is taken out for cooling.
Example 2
The nano matt super wear-resistant diamond glaze comprises the following raw material components in parts by weight:
12 parts of kaolin;
5 parts of quartz sand;
15 parts of diopside;
20 parts of basalt;
5 parts of aluminum oxide;
3 parts of cordierite;
16 parts of cordierite type matte frit powder;
5 parts of nepheline syenite;
7 parts of calcined zinc oxide.
Wherein: formation of cordierite type matt frit powderThe chemical composition comprises the following components in percentage by weight: siO (SiO) 2 47%，Al 2 O 3 23.2%，K 2 O 2.5%，Na 2 O1.8%, caO 3.5%, mgO 20%, znO 2%. SiO in chemical composition of cordierite type matte frit powder 2 With Al 2 O 3 The molar ratio of (3) to (4): 1.
the basalt comprises the following chemical components in parts by weight: siO (SiO) 2 48.0%，Al 2 O 3 13.4%，K 2 O 1.6%，Na 2 O 3.1%，CaO 14.8%，MgO 15.3%，P 2 O 5 1.0%，Fe 2 O 3 0.2%，FeO 0.4%，MnO 0.2%，TiO 2 2.0%。
The diopside comprises the following chemical compositions in parts by weight: siO (SiO) 2 54.1%，Al 2 O 3 1.5%，K 2 O 0.8%，Na 2 O 0.1%，CaO 22.3%，MgO 20.2%，Fe 2 O 3 0.5%，FeO 0.5%。
The chemical composition of nepheline syenite comprises the following components in parts by weight: siO (SiO) 2 57.2%，Al 2 O 3 24.0%，K 2 O 6.8%，Na 2 O 9.8%，CaO 0.8%，MgO 0.3%，Fe 2 O 3 0.8%，TiO 2 0.3%。
The preparation method of the nano matte super wear-resistant ceramic tile comprises the following steps:
(1) Mixing raw materials for preparing cordierite matte frit powder according to a raw material ratio, melting at 1450 ℃ for 8 hours, pouring into water, and quenching to obtain frit particles; then crushing the frit particles to obtain cordierite type matte frit powder with fineness of 100 meshes;
(2) Mixing the cordierite-type matte frit powder prepared in the step (1) with other raw materials according to the proportion of the raw materials, adding water for ball milling (the mass ratio of the raw materials to the water is 100:40), and obtaining the nano matte super wear-resistant diamond glaze with the fineness of 325 meshes and 0.3 weight percent of screen residue;
(3) Mixing the raw materials of the ground glaze layer according to a proportion, adding water for ball milling (the mass ratio of the raw materials to the water is 100:40), and obtaining the ground glaze with the fineness of 325 meshes and 0.3 weight percent of screen residue;
(4) Spraying the base glaze prepared in the step (3) on the green body, printing a decorative pattern by ink jet, spraying the nano matte super-wear-resistant diamond glaze prepared in the step (2) to form a base glaze layer, an ink jet printing pattern layer and a diamond glaze layer, and drying and sintering to obtain the nano matte super-wear-resistant ceramic tile of the embodiment, wherein the thickness of the diamond glaze layer is 0.12mm.
The firing temperature system is as follows: firstly, raising the temperature to 950 ℃ at a heating rate of 18 ℃/min, and preserving the temperature for 15min; then the temperature is increased to 1150 ℃ at the heating rate of 9 ℃/min, the heat is preserved for 8min, and finally the kiln is taken out for cooling.
Example 3
The nano matt super wear-resistant diamond glaze comprises the following raw material components in parts by weight:
14 parts of kaolin;
6 parts of quartz sand;
12 parts of diopside;
28 parts of basalt;
6 parts of aluminum oxide;
5 parts of cordierite;
20 parts of cordierite type matte frit powder;
6 parts of nepheline syenite;
5 parts of calcined zinc oxide.
Wherein: the chemical composition of the cordierite type matte frit powder comprises the following components in percentage by weight: siO (SiO) 2 46.8%，Al 2 O 3 25.2%，K 2 O 2%，Na 2 O2%, caO 3%, mgO 17% and ZnO 4%. SiO in chemical composition of cordierite type matte frit powder 2 With Al 2 O 3 The molar ratio of (3) is 3.1:1.
the basalt comprises the following chemical components in parts by weight: siO (SiO) 2 46.5%，Al 2 O 3 13.8%，K 2 O 2.2%，Na 2 O 2.6%，CaO 15.3%，MgO 14.1%，P 2 O 5 1.2%，Fe 2 O 3 0.4%，FeO 0.6%，MnO 0.3%，TiO 2 3.0%。
The diopside comprises the following chemical compositions in parts by weight: siO (SiO) 2 53.4%，Al 2 O 3 2.0%，K 2 O 0.8%，Na 2 O 0.1%，CaO 21.6%，MgO 21.3%，Fe 2 O 3 0.4%，FeO 0.4%。
The chemical composition of nepheline syenite comprises the following components in parts by weight: siO (SiO) 2 57.2%，Al 2 O 3 24.0%，K 2 O 6.8%，Na 2 O 9.8%，CaO 0.8%，MgO 0.3%，Fe 2 O 3 0.8%，TiO 2 0.3%。
The preparation method of the nano matte super wear-resistant ceramic tile comprises the following steps:
(1) Mixing raw materials for preparing cordierite matte frit powder according to a raw material ratio, melting for 9 hours at 1500 ℃, pouring into water, quenching to obtain frit particles; then crushing the frit particles to obtain cordierite type matte frit powder with fineness of 100 meshes;
(2) Mixing the cordierite-type matte frit powder prepared in the step (1) with other raw materials according to the proportion of the raw materials, adding water for ball milling (the mass ratio of the raw materials to the water is 100:40), and obtaining the nano matte super wear-resistant diamond glaze with the fineness of 325 meshes and 0.4 weight percent of screen residue;
(3) Mixing the raw materials of the ground glaze layer according to a proportion, adding water for ball milling (the mass ratio of the raw materials to the water is 100:40), and obtaining the ground glaze with the fineness of 325 meshes and 0.5 weight percent of screen residue;
(4) Spraying the base glaze prepared in the step (3) on the green body, printing a decorative pattern by ink jet, spraying the nano matte super-wear-resistant diamond glaze prepared in the step (2) to form a base glaze layer, an ink jet printing pattern layer and a diamond glaze layer, and drying and sintering to obtain the nano matte super-wear-resistant ceramic tile of the embodiment, wherein the thickness of the diamond glaze layer is 0.15mm.
The firing temperature system is as follows: firstly, heating to 980 ℃ at a heating rate of 15 ℃/min, and preserving heat for 15min; then the temperature is increased to 1180 ℃ at the heating rate of 10 ℃/min, the temperature is kept for 10min, and finally the kiln is taken out for cooling.
Example 4
The nano matt super wear-resistant diamond glaze comprises the following raw material components in parts by weight:
15 parts of kaolin;
5 parts of quartz sand;
20 parts of diopside;
20 parts of basalt;
10 parts of aluminum oxide;
6 parts of cordierite;
15 parts of cordierite type matte frit powder;
7 parts of nepheline syenite;
6 parts of calcined zinc oxide.
Wherein: the chemical composition of the cordierite type matte frit powder comprises the following components in percentage by weight: siO (SiO) 2 48.3%，Al 2 O 3 24.6%，K 2 O 2%，Na 2 O1%, caO 3.1%, mgO 18% and ZnO 3%. SiO in chemical composition of cordierite type matte frit powder 2 With Al 2 O 3 The molar ratio of (3) is 3.3:1.
the basalt comprises the following chemical components in parts by weight: siO (SiO) 2 46.7%，Al 2 O 3 13.4%，K 2 O 1.6%，Na 2 O 3.1%，CaO 15.9%，MgO 15.3%，P 2 O 5 1.0%，Fe 2 O 3 0.3%，FeO 0.5%，MnO 0.2%，TiO 2 2.0%。
The diopside comprises the following chemical compositions in parts by weight: siO (SiO) 2 53.4%，Al 2 O 3 2.0%，K 2 O 0.8%，Na 2 O 0.1%，CaO 21.6%，MgO 21.3%，Fe 2 O 3 0.4%，FeO 0.4%。
The chemical composition of nepheline syenite comprises the following components in parts by weight: siO (SiO) 2 57.8%，Al 2 O 3 23.9%，K 2 O 6.5%，Na 2 O 9.3%，CaO 0.9%，MgO 0.2%，Fe 2 O 3 1.0%，TiO 2 0.4%。
The preparation method of the nano matte super wear-resistant ceramic tile comprises the following steps:
(1) Mixing raw materials for preparing cordierite matte frit powder according to a raw material ratio, melting at 1500 ℃ for 10 hours, pouring into water, quenching to obtain frit particles; then crushing the frit particles to obtain cordierite type matte frit powder with fineness of 100 meshes;
(2) Mixing the cordierite-type matte frit powder prepared in the step (1) with other raw materials according to the proportion of the raw materials, adding water for ball milling (the mass ratio of the raw materials to the water is 100:40), and obtaining the nano matte super wear-resistant diamond glaze with the fineness of 325 meshes and 0.5 weight percent of screen residue;
(3) Mixing the raw materials of the ground glaze layer according to a proportion, adding water for ball milling (the mass ratio of the raw materials to the water is 100:40), and obtaining the ground glaze with the fineness of 325 meshes and 0.3 weight percent of screen residue;
(4) Spraying the base glaze prepared in the step (3) on the green body, printing a decorative pattern by ink jet, spraying the nano matte super-wear-resistant diamond glaze prepared in the step (2) to form a base glaze layer, an ink jet printing pattern layer and a diamond glaze layer, and drying and sintering to obtain the nano matte super-wear-resistant ceramic tile of the embodiment, wherein the thickness of the diamond glaze layer is 0.12mm.
The firing temperature system is as follows: firstly, raising the temperature to 1000 ℃ at a heating rate of 18 ℃/min, and preserving the temperature for 15min; then the temperature is increased to 1200 ℃ at the heating rate of 8 ℃/min, the temperature is kept for 10min, and finally the kiln is taken out for cooling.
Comparative example 1
Comparative example 1 differs from example 1 only in that: the raw material components of the nano matte super wear-resistant diamond glaze of comparative example 1 are not added with cordierite, and the types and the addition amounts of other raw materials and the preparation method of the nano matte super wear-resistant ceramic tile are the same as those of example 1.
Comparative example 2
Comparative example 2 differs from example 1 only in that: the raw material components of the nano matte super wear-resistant diamond glaze of comparative example 2 adopt equal amounts of talcum and dolomite to replace basalt and diopside in example 1 respectively, and the types and the addition amounts of other raw materials and the preparation method of the nano matte super wear-resistant ceramic tile are the same as those of example 1.
Comparative example 3
Comparative example 3 differs from example 1 only in that: the raw material components of the nano matte super wear-resistant diamond glaze of the comparative example 3 are
The same amount of feldspar was used instead of nepheline syenite in example 1, and the types and addition amounts of other raw materials were the same as in example 1.
Comparative example 4
Comparative example 4 differs from example 1 only in that: the raw material components of the nano matte super wear-resistant diamond glaze of comparative example 4 are not added with calcined zinc oxide, and the types and the addition amounts of other raw materials and the preparation method of the nano matte super wear-resistant ceramic tile are the same as those of example 1.
Comparative example 5
Comparative example 5 differs from example 1 only in that: in the preparation method of the nano matte super wear-resistant ceramic tile in comparative example 5, one-time heating sintering is adopted, and the specific sintering schedule is as follows: raising the temperature to 1160 ℃ at a heating rate of 16 ℃/min, preserving the heat for 30min, and finally taking out from the kiln for cooling.
Performance detection
The nano matt super wear resistant ceramic tile samples prepared in examples 1-4 and comparative examples 1-5 were subjected to Mohs hardness, wear resistance, glossiness and transmittance performance test of the diamond glaze. Wherein: the wear resistance is detected according to GB/T3810.7-2016 'determination of the wear resistance of the surface of a glazed ceramic brick'; transmittance the visible light transmittance of the diamond glaze was measured according to GB2680-2021 "measurement of visible light transmittance, solar direct transmittance, solar total transmittance, ultraviolet transmittance and related glazing parameters of architectural glass", and the test results are shown in Table 1.
Table 1: comparative Table of Properties of samples prepared in examples 1 to 4 and comparative examples 1 to 5
As can be seen from Table 1, the ceramic tile samples prepared in examples 1-4 of the present invention had gloss values of 8-13℃and a matte gloss; the Mohs hardness can reach 7-7.5, the wear resistance can reach 5 levels, the rotation speed is 15000, and the wear-resistant rubber has the characteristics of high hardness and high wear resistance; and the visible light transmittance of the diamond glaze layer reaches 68-72%, and the color development performance is good.
Comparative examples 1-2 compared to example 1, since cordierite was not added as seeding agent or talc and dolomite were used instead of basalt and diopside, the hardness and abrasion resistance of the product were significantly reduced as compared to example 1.
Comparative examples 3-4 the light transmittance of the diamond glaze was significantly reduced and the hardness and abrasion resistance were also reduced compared to example 1, due to the use of nepheline syenite instead of conventional feldspar or without the addition of calcined zinc oxide.
In comparative example 5, since the primary firing at a temperature was employed, crystals were not sufficiently precipitated and the crystal growth phenomenon occurred, the glossiness was high and the light transmittance, hardness and abrasion resistance were inferior to those of example 1.
In addition, the nano matte super wear-resistant ceramic tile of each embodiment and the comparative example of the present invention has a structure as shown in fig. 1 to 3, and comprises a green body 100 and a diamond glaze layer, wherein the diamond glaze layer is arranged on the upper surface of the green body 100, specifically, the diamond glaze layer and the green body 100 are connected through a glaze spraying process, and the thickness of the diamond glaze layer is uniform, preferably an electrostatic glaze spraying process. The diamond glaze layer is formed by firing the nano matte super-wear-resistant diamond glaze of the embodiment. The specific structural design surrounding the blank 100 will be described below.
It will be appreciated that fig. 1 and 3 are only schematic illustrations of a portion of the blank 100 cut away to clearly illustrate the structural design of the blank 100.
As shown in fig. 1 and 2, the blank 100 is provided with a protrusion 200 and a recess 300. Specifically, the upper surface of the blank 100 is recessed downward to form the recess 300, and the upper surface of the blank 100 is raised upward to form the protrusion 200. It will be appreciated that the protrusion 200 is above the upper surface of the blank 100 and the recess 300 is below the upper surface of the blank 100.
The number of the protrusions 200 is plural, and all the protrusions 200 are arranged in the lateral direction and the longitudinal direction of the blank 100, respectively, as shown in fig. 1, and all the protrusions 200 are arranged in an array in a plan view. The shape of the convex portion 200 may be prismatic, cylindrical, or hemispherical. In the present embodiment, the plurality of protrusions 200 are arranged at uniform intervals along the lateral direction of the blank 100; also, the plurality of protrusions 200 are disposed at uniform intervals along the longitudinal direction of the blank 100. The convex part 200 adopts a hemispherical design, so that the nano matte super wear-resistant ceramic tile can be uniformly and reasonably stressed, and the material strength can be fully utilized.
The number of the grooves 300 is plural, and all the grooves 300 are arranged in the lateral direction and the longitudinal direction of the blank 100, respectively, as shown in fig. 1, and all the grooves 300 are arranged in an array in a plan view. The shape of the recess 300 may be cylindrical, hemispherical, or prismatic. In the present embodiment, the plurality of grooves 300 are provided at uniform intervals along the lateral direction of the blank 100; also, a plurality of grooves 300 are provided at uniform intervals along the longitudinal direction of the blank 100. The groove 300 adopts a hemispherical shape design, so that the stress of the nano matte super wear-resistant ceramic tile is more uniform and reasonable, and the material strength can be fully utilized.
A groove 300 is arranged between any two adjacent convex parts 200 as seen in the transverse direction of the blank 100, and at this time, the centers of the convex parts 200 and the groove 300 are positioned on the same transverse extension line; a groove 300 is provided between any adjacent two of the protrusions 200, as seen in the longitudinal direction of the blank 100, wherein the protrusions 200 and the center of the groove 300 are on the same longitudinal extension. As shown in fig. 1, at a non-edge position of the blank 100, a recess 300 is provided around each protrusion 200, and a protrusion 200 is provided around each recess 300. In the present embodiment, the X direction is assumed to be the lateral direction of the green body 100, the Y direction is assumed to be the longitudinal direction of the green body 100, and the Z direction is assumed to be the vertical direction of the green body 100.
It will be appreciated that, as shown in fig. 2, there is a certain gap between the recess 300 and the protrusion 200, and the gap may be set according to the actual situation. For example, in some embodiments, the gap can range in value from 0mm to 4mm.
In the case of hemispherical designs, the dimensions of the recess 300 and the protrusion 200 may be the same or different. For example, the size of the recess 300 may be greater than or less than the size of the protrusion 200.
The size of the protrusion 200 and the size of the recess 300 may be designed according to practical situations. For example, in some embodiments, the diameter of the protrusion 200 and the recess 300 ranges from 2mm to 6mm. In the present embodiment, the diameter of the convex portion 200 and the diameter of the concave groove 300 are both set to 4mm, and the gap between the convex portion 200 and the concave groove 300 is 2mm.
It will be appreciated that the connection between the recess 300 and the upper surface of the blank 100 may be of a rounded transition design. Likewise, the connection between the protrusion 200 and the upper surface of the blank 100 may also be designed with a rounded transition.
The plurality of convex parts 200 are arranged on the green body 100, so that the surface friction coefficient of the nano matte super wear-resistant ceramic tile can be increased, the friction force between the nano matte super wear-resistant ceramic tile and shoes is enhanced, and the phenomenon that people slip easily is avoided. When the convex parts 200 on the green body 100 are excessively worn, the grooves 300 arranged on the green body 100 can still ensure that the nano matte super wear-resistant ceramic bricks have high surface friction coefficients, can still ensure that strong friction effect is generated between the nano matte super wear-resistant ceramic bricks and shoes, and prevent people from slipping easily.
The blank 100 is simultaneously provided with a plurality of convex parts 200 and a plurality of grooves 300, so that the nano matte super wear-resistant ceramic tile has double anti-skid functions. The convex parts 200 and the grooves 300 are arranged in an array manner, so that the nano matte super wear-resistant ceramic tile can play an excellent anti-skid effect in 360 degrees all directions. In addition, the number of the protrusions 200 and the recesses 300 is maximized, so that the protrusions 200 and the recesses 300 are uniformly distributed on the blank 100. The blank 100 adopts such unique structure and is matched with the diamond glaze layer made of the nano matte super wear-resistant diamond glaze, so that the anti-skid and wear-resistant performances of the nano matte super wear-resistant ceramic tile can be greatly enhanced, the convex parts 200 on the blank 100 are promoted to be difficult to wear, the nano matte super wear-resistant ceramic tile can play an excellent anti-skid role for a long time, and the service life of the nano matte super wear-resistant ceramic tile can be prolonged.
When water marks appear on the upper surface of the nano matte super wear-resistant ceramic tile, water flows to the grooves 300 on the green body 100, and the grooves 300 provide a certain space for containing water. Moreover, when the water in the groove 300 overflows, the water overflows into the adjacent groove 300, so that the upper surface of the blank 100 is free from water accumulation, and the condition that people easily slip can be prevented.
In another embodiment, as shown in fig. 3, a drainage groove 400 is disposed between any two adjacent grooves 300, the drainage groove 400 bypasses the convex portion 200, and the two grooves 300 are communicated through the drainage groove 400, so that water in one groove 300 can overflow into the adjacent groove 300 through the drainage groove 400, and therefore, water on the nano matte super wear-resistant ceramic tile can be easily diffused to more grooves 300; the drainage groove 400 can avoid water accumulation on the upper surface of the nano matte super wear-resistant ceramic tile in the water diffusion process, and promote the dry upper surface of the nano matte super wear-resistant ceramic tile, that is, the problem that the dry upper surface of the blank 100 is wetted due to upward water rushing to the upper surface of the blank 100 in the groove 300 and people easily slip is avoided.
In the present embodiment, the acute angle formed between the extending direction of the drainage groove 400 and the lateral direction of the blank 100 is 45 °. At this time, the drainage groove 400 is located between two adjacent protrusions 200. Also, the extending direction of the drainage groove 400 passes through the center position of the groove 300.
It is understood that the cross-sectional shape of the drainage channel 400 may be square or U-shaped or hemispherical. The depth of the drainage groove 400 is less than or equal to the depth of the recess 300. The cross-sectional dimension of the drainage channel 400 is less than or equal to the diameter of the recess 300. In this embodiment, the depth of the drainage groove 400 may be set to 2mm, and the cross-sectional dimension of the drainage groove 400 is 2mm.
Further, for the groove 300 disposed near the edge of the blank 100, the drainage groove 400 of the groove 300 extends to the edge of the blank 100, so as to guide water to the edge of the blank 100, to avoid wetting the dry upper surface of the blank 100, and at this time, the drainage groove 400 may extend along the lateral direction, the longitudinal direction or the oblique direction of the blank 100.
Furthermore, the edge angle between the upper surface and the side surface of the green body 100 adopts the arc transition design, so that after the nano matte super wear-resistant ceramic bricks are paved, a water collecting tank is formed between two adjacent nano matte super wear-resistant ceramic bricks, and therefore, water in the groove 300 can be guided into the water collecting tank through the drainage tank 400, and the nano matte super wear-resistant ceramic bricks can have better anti-skid effect.
It will be appreciated that the blank 100 of the above construction may be formed by a press forming process.
It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the inventive concept. Accordingly, it is intended that all such modifications as would be within the scope of this invention be included within the scope of this invention. The above embodiments are preferred embodiments of the present invention, and all similar processes and equivalent modifications are intended to fall within the scope of the present invention.
Claims (9)
1. The nano matte super wear-resistant diamond glaze is characterized by comprising the following raw materials in parts by weight:
10-15 parts of kaolin;
3-6 parts of quartz sand;
10-20 parts of diopside;
20-30 parts of basalt;
5-10 parts of aluminum oxide;
3-6 parts of cordierite;
15-20 parts of cordierite type matte frit powder;
10-15 parts of a color-developing regulator;
the color-development regulator comprises nepheline syenite and calcined zinc oxide;
the cordierite-type matte frit powder comprises the following chemical components in percentage by weight: siO (SiO) 2 40-50%，Al 2 O 3 20-30%，K 2 O 2-3%，Na 2 O 1-2%，CaO 3-4%，MgO 15-20%，ZnO 2-4%。
2. The nano-matte super abrasive diamond glaze according to claim 1, wherein the chemical composition of the cordierite-type matte frit powder is SiO 2 With Al 2 O 3 The molar ratio of (3-4): 1.
3. the nano-matte super abrasive diamond glaze according to claim 1, wherein the mass ratio of nepheline syenite to calcined zinc oxide is (0.5-1.2): 1.
4. the nano matte super abrasive diamond glaze according to claim 1, wherein the bastard armsThe chemical composition of the rock comprises the following components in percentage by weight: siO (SiO) 2 44-48%，Al 2 O 3 12-14%，K 2 O 1-3%，Na 2 O 2-4%，CaO14-18%，MgO12-16%，P 2 O 5 0.8-1.4%，Fe 2 O 3 0.2-0.4%，FeO 0.3-0.6%，MnO 0.2-0.4%，TiO 2 1-4%; the diopside comprises the following chemical components in percentage by weight: siO (SiO) 2 52-55%，Al 2 O 3 1-2%，K 2 O 0.7-0.9%，Na 2 O 0.1-0.2%，CaO 21-24%，MgO 20-22%，Fe 2 O 3 0.4-0.6%, feO 0.4-0.6%; the chemical composition of the nepheline syenite comprises the following components in percentage by weight: siO (SiO) 2 55-60%，Al 2 O 3 20-25%，K 2 O 5-10%，Na 2 O 8-10%，CaO 0.8-1.0%，MgO 0.1-0.4%，Fe 2 O 3 0.8-1.1%，TiO 2 0.3-0.5%。
5. A method for preparing a nano matt super wear resistant diamond glaze, which is used for preparing the nano matt super wear resistant diamond glaze according to any one of claims 1 to 4, and comprises the following steps:
(1) Mixing raw materials for preparing cordierite type matte frit powder, pouring the mixture into water for quenching after melting, wherein the melting temperature is 1450-1500 ℃, and the melting time is 8-10 hours, so as to obtain frit particles; then crushing the frit particles to obtain cordierite type matte frit powder;
(2) Mixing the cordierite-type matt frit powder with other raw materials for preparing the nano matt super-wear-resistant diamond glaze, and performing wet ball milling to obtain the nano matt super-wear-resistant diamond glaze.
6. The nano matte super wear-resistant ceramic tile is characterized by comprising a blank and a diamond glaze layer arranged on the upper surface of the blank, wherein the diamond glaze layer is formed by firing the nano matte super wear-resistant diamond glaze according to any one of claims 1 to 4;
the firing temperature system is as follows: firstly, raising the temperature to 950-1000 ℃ at the temperature raising rate of 15-18 ℃/min, and preserving the heat for 10-15min; then the temperature is increased to the highest firing temperature at the heating rate of 8-10 ℃/min, the temperature is kept for 8-10min, and finally the kiln is taken out for cooling; the highest sintering temperature is 1150-1200 ℃.
7. The nano matte super wear-resistant ceramic tile according to claim 6, wherein the upper surface of the green body is provided with a plurality of protrusions and a plurality of grooves, all the protrusions are respectively arranged along the transverse direction and the longitudinal direction of the green body, all the grooves are respectively arranged along the transverse direction and the longitudinal direction of the green body, and the grooves are arranged between any two adjacent protrusions in the transverse direction and the longitudinal direction of the green body.
8. The nano matte super abrasive ceramic tile according to claim 6, wherein the diamond glaze layer has a thickness of 0.1-0.15mm.
9. A method for preparing a nano-matt super wear-resistant ceramic tile according to any one of claims 6 to 8, comprising the steps of:
(1) The method for preparing nano matt super wear-resistant diamond glaze according to claim 5;
(2) Applying the diamond glaze on a blank body to form a diamond glaze layer, and drying and sintering to obtain the nano matte super wear-resistant ceramic tile;
the firing temperature system is as follows: firstly, raising the temperature to 950-1000 ℃ at the temperature raising rate of 15-18 ℃/min, and preserving the heat for 10-15min; then the temperature is increased to the highest firing temperature at the heating rate of 8-10 ℃/min, the temperature is kept for 8-10min, and finally the kiln is taken out for cooling; the highest sintering temperature is 1150-1200 ℃.
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