CN114772933B - Nano soft super-wear-resistant diamond glaze and ceramic tile and preparation method thereof - Google Patents
Nano soft super-wear-resistant diamond glaze and ceramic tile and preparation method thereof Download PDFInfo
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- CN114772933B CN114772933B CN202210708227.6A CN202210708227A CN114772933B CN 114772933 B CN114772933 B CN 114772933B CN 202210708227 A CN202210708227 A CN 202210708227A CN 114772933 B CN114772933 B CN 114772933B
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- glaze
- zirconium
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- ceramic tile
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- 239000010432 diamond Substances 0.000 title claims abstract description 115
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 115
- 239000000919 ceramic Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 111
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 111
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims abstract description 85
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000000126 substance Substances 0.000 claims abstract description 40
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 37
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 34
- 239000013078 crystal Substances 0.000 claims description 105
- 238000010304 firing Methods 0.000 claims description 60
- 235000012239 silicon dioxide Nutrition 0.000 claims description 40
- 239000002994 raw material Substances 0.000 claims description 39
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 37
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 37
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000005995 Aluminium silicate Substances 0.000 claims description 20
- 235000012211 aluminium silicate Nutrition 0.000 claims description 20
- 239000012752 auxiliary agent Substances 0.000 claims description 20
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 20
- 239000002002 slurry Substances 0.000 claims description 19
- 239000006060 molten glass Substances 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 17
- 238000000498 ball milling Methods 0.000 claims description 15
- 239000011575 calcium Substances 0.000 claims description 15
- 229910052791 calcium Inorganic materials 0.000 claims description 15
- 239000011777 magnesium Substances 0.000 claims description 15
- 229910052749 magnesium Inorganic materials 0.000 claims description 15
- 239000011701 zinc Substances 0.000 claims description 15
- 229910052725 zinc Inorganic materials 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003638 chemical reducing agent Substances 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 12
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- 238000007641 inkjet printing Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 229910052712 strontium Inorganic materials 0.000 claims description 11
- 229920000609 methyl cellulose Polymers 0.000 claims description 9
- 239000001923 methylcellulose Substances 0.000 claims description 9
- 235000010981 methylcellulose Nutrition 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 6
- 238000005299 abrasion Methods 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 239000012744 reinforcing agent Substances 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 3
- 230000003373 anti-fouling effect Effects 0.000 abstract description 14
- 238000011161 development Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 12
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 42
- 239000011734 sodium Substances 0.000 description 33
- 239000011787 zinc oxide Substances 0.000 description 21
- 230000006872 improvement Effects 0.000 description 15
- 238000005245 sintering Methods 0.000 description 13
- 239000011449 brick Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000004576 sand Substances 0.000 description 8
- 239000000454 talc Substances 0.000 description 7
- 229910052623 talc Inorganic materials 0.000 description 7
- 229910052845 zircon Inorganic materials 0.000 description 7
- 230000001795 light effect Effects 0.000 description 6
- 229910052882 wollastonite Inorganic materials 0.000 description 6
- 239000010456 wollastonite Substances 0.000 description 6
- 229910021532 Calcite Inorganic materials 0.000 description 5
- 229910052656 albite Inorganic materials 0.000 description 5
- 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
- 229910000514 dolomite Inorganic materials 0.000 description 5
- 239000010459 dolomite Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 210000003298 dental enamel Anatomy 0.000 description 3
- 239000010433 feldspar Substances 0.000 description 3
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910000018 strontium carbonate Inorganic materials 0.000 description 3
- 241000322338 Loeseliastrum Species 0.000 description 2
- GEIAQOFPUVMAGM-UHFFFAOYSA-N Oxozirconium Chemical compound [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910001570 bauxite Inorganic materials 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007688 edging Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910001427 strontium ion Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000016776 visual perception Effects 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/20—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing titanium compounds; containing zirconium compounds
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
-
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- 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
- C04B35/14—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 silica
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- 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
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- 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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- 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
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- 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
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- 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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- 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
- C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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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
- C04B2235/963—Surface properties, e.g. surface roughness
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Abstract
The invention relates to the field of building ceramic materials, and particularly discloses a nano subdued light super-wear-resistant diamond glaze, a ceramic tile and a preparation method thereof, wherein the diamond glaze comprises the following chemical compositions: SiO 2 2 50.00~59.00%，Al 2 O 3 11.00~26.00%，K 2 O+Na 2 O=5.00~9.30%，CaO+MgO+SrO+ZnO=12.00~31.00%，ZrO 2 3.00~6.50%，SiO 2 /Al 2 O 3 =2.5~4.5，K 2 O/Na 2 O =1.1 to 3.0; the diamond glaze coexists with nano-zirconia grains, zirconium silicate grains and zirconium-containing M-silicate grains. Correspondingly, the invention also discloses the nano soft light super wear-resistant ceramic tile and a preparation method thereof. The invention can simultaneously realize high hardness, good wear resistance, good antifouling property, ideal color development and good light softening effect.
Description
Technical Field
The invention relates to the technical field of building ceramic materials, in particular to nano soft super wear-resistant diamond glaze, ceramic tile and a preparation method thereof.
Background
Glazes capable of exhibiting a mercerized or jade-like luster without intense reflected light are generally referred to as matt glazes or soft glazes in the ceramic tile and rock plate markets. The soft tile has the advantages that the tile surface is fine and smooth, moist and free of strong light reflection, soft, quiet and comfortable visual perception is brought to people, the soft, quiet and comfortable tile has simple, natural and elegant artistic characteristics, meanwhile, the soft tile is worried about the healthy atmosphere without light pollution, the light reflection of the tile is controlled at the soft light level of 22-30 degrees according to the spatial refraction rule, the spatial light sensation is moderate in light and shade, a comfortable light sensing state is created for eyes, the fatigue hidden danger is avoided, and therefore special texture and special artistic charm are brought to products and are favored by users. The application aims to provide a glaze material with good soft light effect and comprehensive performance.
The research on the soft light tiles mainly focuses on the aspects of how to make the gloss of the soft light glaze more stable and the color development better, but the abrasion resistance and the hardness of the glaze are rarely involved. With the gradual popularization and application of the soft glaze product, the soft glaze product has the defects of easy occurrence of frosting, scratches, easy dirtiness and the like in the production and use processes.
The prior art 1 is a Chinese patent document CN107344814A, and discloses a soft glaze and a soft brick, wherein the glaze mainly comprises 50-60 parts of frit, 8-20 parts of kaolin, 20-35 parts of potassium feldspar, 10-20 parts of wollastonite, 8-15 parts of zirconium oxide, 1-5 parts of zinc oxide and 40-60 parts of water. Various composition synergism of sheen brick overglaze, the glaze slip of gained is even, and is mobile good, the sheen brick is through inciting somebody to action in the manufacturing process the three-quarter spraying of sheen brick overglaze volume of application is on the underglaze coat, and remaining quarter spraying has removed the use protection glaze from on the calico printing layer, the sheen brick uses the sheen brick overglaze utilizes above-mentioned manufacturing method to make the sheen brick finished product, has solved the uncontrollable problem of sheen brick glossiness, with the difference control of sheen brick surface gloss degree in 10 to the colour that makes the calico printing layer on the ceramic tile is than using general sheen brick overglaze more bright-coloured on the market. However, the prior art 1 only solves the technical problem of the uniformity of the glossiness, and cannot simultaneously solve a plurality of technical problems of the soft glaze, such as good color development effect, wear resistance and antifouling property.
Disclosure of Invention
The invention aims to solve the technical problem of providing a nano subdued light super wear-resistant diamond glaze, wherein a glaze layer formed by the diamond glaze has high hardness, good wear resistance, good antifouling property, good transparency and good subdued light effect.
The invention also aims to solve the technical problem of providing the nano soft-light super-wear-resistant diamond glaze ceramic tile and the preparation method thereof, wherein the ceramic tile has the advantages of high hardness, good wear resistance, good antifouling property, ideal color development, good soft light effect and good pattern visualization effect.
In order to achieve the technical effect, the invention provides a nano soft super wear-resistant diamond glaze which comprises the following chemical components in percentage by weight:
SiO 2 50.00~59.00%，Al 2 O 3 11.00~26.00%，K 2 O+Na 2 O=5.00~9.30%，CaO+MgO+SrO+ZnO=12.00~31.00%， ZrO 2 3.00~6.50%，SiO 2 /Al 2 O 3 =2.5~4.5，K 2 O/Na 2 o = 1.1-3.0, and the ignition loss is 0.70-2.01%;
the diamond glaze coexists with nano-zirconia grains, zirconium silicate grains and zirconium-containing silicic acid M grains, wherein M represents any one or combination of calcium, magnesium, strontium and zinc.
As an improvement of the scheme, the grain size of the nano zirconia crystal grain is 300-900 nanometers, the grain size of the zirconium silicate crystal grain is 1-5 micrometers, and the grain size of the zirconium-containing silicic acid M crystal grain is 1-10 micrometers.
As an improvement of the scheme, the grain size of the nano zirconia crystal grain is 500-800 nanometers, the grain size of the zirconium silicate crystal grain is 1-3 micrometers, and the grain size of the zirconium-containing silicic acid M crystal grain is 3-6 micrometers.
As an improvement of the scheme, the glossiness of the nanometer soft super wear-resistant diamond glaze is 15-30 degrees.
As an improvement of the scheme, the nano soft super wear-resistant diamond glaze mainly comprises the following raw materials in parts by weight: 80-95 parts of zirconium-containing frit, 0.1-10 parts of zirconium silicate, 0.1-10 parts of zirconium oxide, 1-20 parts of kaolin and 0.1-5 parts of auxiliary agent.
As an improvement of the above scheme, the chemical composition of the zirconium-containing frit comprises: SiO 2 2 50.00~60.00%，Al 2 O 3 9.50~20.00%，CaO+MgO+SrO+ZnO=18.00~30.00%，K 2 O+Na 2 O=6.00~10.00%，ZrO 2 3.50~5.50%。
As an improvement of the scheme, the nano soft light super wear-resistant diamond glaze is sintered under the following conditions: the firing period is 30-180 minutes; the highest firing temperature is 1190-1220 ℃, and the heat preservation time of the highest firing temperature is 5-20 minutes;
the time required for cooling from the maximum firing temperature to 950-1050 ℃ is 15-35 minutes.
On the other hand, the invention also provides a nanometer subdued light super-wear-resistant ceramic tile which comprises a ceramic tile blank and a diamond glaze layer arranged on the ceramic tile blank, wherein the diamond glaze layer is made of the nanometer subdued light super-wear-resistant diamond glaze.
As an improvement of the scheme, the thickness of the diamond glaze layer is 10-15 microns.
As an improvement of the scheme, the ceramic tile blank comprises the following chemical components in percentage by weight: SiO 2 2 65~70%，Al 2 O 3 19~21%，CaO+MgO=0.35~0.8%，K 2 O+Na 2 O = 4.5-5.5%, and loss on ignition is 4.5-5.5%.
As an improvement of the scheme, the ceramic tile further comprises a ground coat coated on the ceramic tile blank, wherein the ground coat comprises the following chemical components in percentage by weight: SiO 2 2 60~65%，Al 2 O 3 22~25%，CaO+MgO=0.15~0.50%，K 2 O+Na 2 O=2.5~3.5%，ZnO 1.5~2.0%，ZrO 2 6 to 9 percent, and the ignition loss is 2.5 to 3.3 percent
In another aspect, the invention further provides a preparation method of the nano soft super wear-resistant diamond-glazed ceramic tile, which comprises the following steps:
A. selecting/preparing a ceramic tile blank;
B. selecting/preparing a ground glaze;
C. preparing nano soft super wear-resistant diamond glaze;
D. applying the base glaze on the ceramic tile blank, and carrying out ink-jet printing on patterns;
E. and (3) applying the nano soft super wear-resistant diamond glaze on the ground coat to obtain a diamond glaze layer, drying and firing in a kiln.
As an improvement of the above scheme, step C comprises:
uniformly mixing raw materials containing zirconium frits, adding the raw materials into a frit furnace to be melted into molten glass, and then pouring the molten glass into water to be quenched to obtain the zirconium-containing frits;
adding the raw materials of the nanometer soft super wear-resistant diamond glaze into a ball mill according to the chemical composition of the nanometer soft super wear-resistant diamond glaze, and carrying out ball milling to obtain glaze slurry;
and grinding the glaze slip to obtain the nano glaze slip with the average grain diameter controlled to be less than 900 nanometers.
As an improvement of the scheme, the raw materials of the nano soft super wear-resistant diamond glaze are selected from zirconium-containing frits, zirconium silicate, zirconium oxide, kaolin and an auxiliary agent;
the raw materials of the zirconium-containing frit are selected from one or more of quartz, potassium feldspar, albite, talc, wollastonite, dolomite, calcite, zinc oxide, strontium carbonate, alumina, zirconium silicate and zirconium oxide.
As an improvement of the scheme, in the step E, the firing period is 30-180 minutes;
the highest firing temperature is 1190-1220 ℃, and the heat preservation time of the highest firing temperature is 5-20 minutes;
the time required for cooling from the maximum firing temperature to 950-1050 ℃ is 15-35 minutes.
In the step E, the thickness of the diamond glaze layer is 10-15 microns.
As an improvement of the scheme, the step A comprises the following steps:
according to the chemical component proportion of the ceramic tile blank, ball-milling the ceramic tile blank raw material and the blank auxiliary agent in a ball mill into slurry, and then sieving, deironing and spray-drying the slurry to obtain blank powder with the water content of 5.5-7.5%;
pressing the mixture into blank powder by a press to obtain a wet blank;
and drying the wet blank to obtain the ceramic tile blank.
As an improvement of the scheme, the ceramic tile blank body is made of one or more of black mud, mixed mud, kaolin, high-temperature sand, feldspar, talc and bauxite;
the green body additive is one or more of a water reducing agent and a green body reinforcing agent.
As an improvement of the above scheme, step B comprises:
according to the chemical component proportion of the ground glaze, ball-milling the ground glaze raw material and the ground glaze auxiliary agent into slurry in a ball mill to obtain the ground glaze;
wherein the ground glaze raw material is one or more of quartz, potassium feldspar, albite, talc, wollastonite, dolomite, calcite, zinc oxide, zirconium silicate and kaolin;
the ground glaze auxiliary agent is one or more of a water reducing agent and methyl cellulose.
The implementation of the invention has the following beneficial effects:
the chemical composition of the nano soft-light super-wear-resistant diamond glaze is designed, so that zirconium oxide grains, zirconium silicate grains and zirconium-containing silicic acid M grains are simultaneously separated out from a glaze layer, abnormal growth and growth of the grains are controlled, and the nano zirconium oxide grains, the zirconium silicate grains and the zirconium-containing silicic acid M grains coexist in the glaze. The grain size of the zirconium oxide grain is in nanometer level, and the grain size of the zirconium silicate grain and the zirconium-containing silicic acid M grain is in micron level, so that the diamond glaze has high hardness, good wear resistance, good antifouling property, good transparency and good soft light effect.
The nano soft super wear-resistant ceramic tile comprises a ceramic tile blank and a diamond glaze layer arranged on the ceramic tile blank, wherein the diamond glaze layer is made of the nano soft super wear-resistant diamond glaze. The nano zirconia crystal grains, the zirconium silicate crystal grains and the zirconium-containing silicic acid M crystal grains coexist in the diamond glaze, so that a glaze layer formed by the diamond glaze is very thin, visible light can penetrate easily, sufficient transparency is achieved, a pattern layer below the glaze layer can be presented truly, and the color development effect is good.
Moreover, the invention has excellent hardness, wear resistance and antifouling performance simultaneously by enabling a sufficient number of high-hardness crystal grains (zirconium oxide, zirconium silicate and zirconium-containing silicic acid M) to be in the glaze and controlling the grain sizes of the zirconium oxide crystal grains, the zirconium silicate crystal grains and the zirconium-containing silicic acid M.
The preparation method of the nanometer soft light super-wear-resistant ceramic tile has the advantages of simple process, controllable cost, strong implementability and convenience for industrial popularization and application.
Drawings
FIG. 1 is a flow chart of the preparation method of the nano soft light super wear-resistant diamond glaze ceramic tile of the present invention.
Detailed Description
To make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
The invention provides a nano subdued light super-wear-resistant diamond glaze which comprises the following chemical components in percentage by weight: SiO 2 2 50.00~59.00%，Al 2 O 3 11.00~26.00%，K 2 O+Na 2 O=5.00~9.30%，CaO+MgO+SrO+ZnO=12.00~31.00%，ZrO 2 3.00~6.50%，SiO 2 /Al 2 O 3 =2.5~4.5，K 2 O/Na 2 O = 1.1-3.0, and the loss on ignition is 0.70-2.01%.
Preferably, the nano soft super wear-resistant diamond glaze comprises the following chemical compositions in percentage by weight:
SiO 2 52.00~55.00%，Al 2 O 3 19.00~23.00%，K 2 O+Na 2 O=5.00~6.50%，CaO+MgO+SrO+ZnO=15.00~27.00%，ZrO 2 3.00~4.50%，SiO 2 /Al 2 O 3 =2.5~3.5，K 2 O/Na 2 o = 1.2-2.8, and the loss on ignition is 1.12-1.69%.
More preferably, the nano soft super wear-resistant diamond glaze comprises the following chemical compositions in percentage by weight: SiO 2 2 52.00~53.00%，Al 2 O 3 20.00~21.00%，K 2 O+Na 2 O=5.00~5.50%，CaO+MgO+SrO+ZnO=16.00~22.00%，ZrO 2 3.00~4.00%，SiO 2 /Al 2 O 3 =2.5~3.0，K 2 O/Na 2 O = 1.2-2.5, and loss on ignition is 1.50-1.61%.
SiO of the present application 2 50.00~59.00%，Al 2 O 3 11.00-26.00%, by controlling SiO 2 /Al 2 O 3 The ratio of the above components to the above components can ensure that the nano zirconia crystal grains, the zirconium silicate crystal grains and the zirconium-containing silicate M crystal grains are not melted by excessive flux, and simultaneously provide enough silicon source for the precipitation and growth of the zirconium silicate crystal grains and the zirconium-containing silicate M crystal grains. But when SiO 2 /Al 2 O 3 Is greater thanWhen 4.5, too much silicon and too little aluminum precipitate too many zirconium silicate grains and zirconium-containing M-silicate grains, resulting in a reduction in transparency of the glaze. By controlling K 2 O/Na 2 The ratio of O is more than that of sodium, and the fluxing property of sodium is higher than that of potassium, so that the nano zirconia crystal grains, the zirconium silicate crystal grains and the zirconium-containing silicate M crystal grains can be prevented from being melted by excessive flux. But when K 2 O/Na 2 When O is more than 3, the glaze is burned because the temperature of the glaze is too high due to excessive potassium.
The diamond glaze coexists with nano-zirconia grains, zirconium silicate grains and zirconium-containing silicic acid M grains, wherein M represents any one or combination of calcium, magnesium, strontium and zinc. Wherein, the grain diameter of the zirconium oxide crystal grain is in nanometer level, and the grain diameters of the zirconium silicate crystal grain and the zirconium-containing silicic acid M crystal grain are preferably in micrometer level.
The invention separates out the zirconium oxide crystal grain, the zirconium silicate crystal grain and the zirconium-containing silicic acid M crystal grain in the overglaze at the same time by reasonably adjusting the composition of the diamond glaze, and controls the abnormal growth and growth of the crystal grains, so that the coexisting grain diameter of the glaze is the zirconium oxide crystal grain at the nanometer level, the zirconium silicate crystal grain at the micrometer level and the zirconium-containing silicic acid M crystal grain at the micrometer level. The three crystal grains with different grain diameters are matched, so that the formed glaze layer is very thin, visible light can penetrate easily, sufficient transparency is achieved, a pattern layer below the glaze layer can be presented truly, and the color development effect is good. In addition, the invention coexists with enough high-hardness crystal grains (zirconia, zirconium silicate and zirconium-containing silicate M), controls the grain sizes of the zirconia crystal grains, the zirconium silicate crystal grains and the zirconium-containing silicate M, and further has excellent hardness, wear resistance and antifouling property.
It should be noted that, as long as the particle size of the zirconia crystal grains is in the nanometer level and the particle size of the zirconium silicate crystal grains and the particle size of the zirconium-containing M silicate crystal grains is in the micrometer level, the requirements of hardness, wear resistance, antifouling property and color development of the diamond glaze with the soft light effect can be basically met at the same time. The nanometer level zirconium oxide crystal grains are uniformly dispersed in a network frame formed by micron level zirconium silicate crystal grains, micron level zirconium-containing M crystal grains and base glaze. Thus, the zirconium-containing silicic acid M crystal grains strengthen the basic glaze, the zirconium silicate crystal grains strengthen the glaze frame formed by the zirconium-containing silicic acid M crystal grains and the basic glaze, and the nano-grade zirconium oxide crystal grains finally disperse, strengthen and toughen the network frame glaze layer formed by the micron-grade zirconium silicate crystal grains, the zirconium-containing silicic acid M crystal grains and the basic glaze. The gradual strengthening and toughening mechanism leads to that the hardness and the wear resistance of the glaze layer are obviously improved on the whole.
Further preferably, the grain size of the nano zirconia crystal grains is 300-900 nm, the grain size of the zirconium silicate crystal grains is 1-5 microns, and the grain size of the zirconium-containing silicic acid M crystal grains is 1-10 microns, so that the transparency, hardness, wear resistance, antifouling property and coloring property of the glaze layer can achieve ideal effects.
If the size of the zirconia crystal grains, the zirconium silicate crystal grains and the zirconium-containing silicate M crystal grains is too large, the gloss of the glaze layer is easily lowered, and the antifouling property and the coloring property are also easily deteriorated. If the sizes of the zirconia crystal grains, the zirconium silicate crystal grains and the zirconium-containing silicate M crystal grains are too small, it is difficult to ensure the glossiness thereof, and the hardness is also easily affected, resulting in deterioration of the hardness.
More preferably, the grain size of the nano zirconia crystal grains is 400-800 nanometers, the grain size of the zirconium silicate crystal grains is 1-3 micrometers, and the grain size of the zirconium-containing silicic acid M crystal grains is 1-7 micrometers, so that the transparency, hardness, wear resistance, antifouling property and coloring property of the glaze layer can achieve more ideal effects.
Preferably, the grain size of the nano zirconia crystal grains is 500-800 nanometers, the grain size of the zirconium silicate crystal grains is 1-3 micrometers, and the grain size of the zirconium-containing silicic acid M crystal grains is 3-6 micrometers, so that the transparency, hardness, wear resistance, antifouling property and coloring property of the glaze layer can achieve the most ideal effect.
The glossiness of the nano soft super wear-resistant diamond glaze is 15-30 degrees, preferably 16-25 degrees, and further preferably 16-22 degrees.
Further, the nanometer soft light super wear-resistant diamond glaze mainly comprises the following raw materials in parts by weight: 80-95 parts of zirconium-containing frit, 0.1-10 parts of zirconium silicate, 0.1-10 parts of zirconium oxide, 1-20 parts of kaolin and 0.1-5 parts of auxiliary agent.
Preferably, the nano soft super wear-resistant diamond glaze mainly comprises the following raw materials in parts by weight: 82-92 parts of zirconium-containing frit, 0.1-5 parts of zirconium silicate, 0.1-5 parts of zirconium oxide, 5-15 parts of kaolin and 0.1-5 parts of auxiliary agent.
Preferably, the nano soft super wear-resistant diamond glaze mainly comprises the following raw materials in parts by weight: 82-92 parts of zirconium-containing frit, 0.5-3 parts of zirconium silicate, 0.5-3 parts of zirconium oxide, 5-15 parts of kaolin and 0.1-3 parts of auxiliary agent.
Wherein, ZrO of the zirconium-containing frit 2 The content is 3.50-5.50%.
The auxiliary agent is one or a combination of a water reducing agent and methylcellulose.
The invention provides three existing forms of zirconium, namely, a zirconium-containing frit, zirconium silicate and zirconium oxide, wherein the states of the zirconium in the three forms are different, wherein the zirconium in the frit is in an ionic state, the zirconium in the zirconium silicate is in a silicon-oxygen tetrahedral lattice of a zircon grain, and the zirconium in the zirconium oxide is in a zirconium-oxygen face-centered cubic lattice formed by oxygen. The zirconium in the zirconium oxygen face-centered cubic lattice can be converted into monoclinic system, tetragonal system and cubic system at any time under the influence of the surrounding environment (the components and the proportion of each element) and the temperature. Zirconium in zirconium silicate is relatively stable, and zirconium in clinker and zirconium oxide is easy to generate crystal transformation or react with surrounding calcium, magnesium, zinc and strontium ions.
Therefore, the invention designs the composition of the diamond glaze and is matched with the sintering process to better control the type, content and size of the precipitated crystal grains. Preferably, the firing period is 30-180 minutes, the maximum firing temperature is 1190-1220 ℃, and the heat preservation time of the maximum firing temperature is 5-20 minutes; the time required for cooling from the highest firing temperature to 950-1050 ℃ is 15-35 minutes, and the coexisting zirconium oxide crystal grains with the grain size of 500-800 nanometers, zirconium silicate crystal grains with the grain size of 1-3 micrometers and zirconium-containing silicate M crystal grains with the grain size of 3-6 micrometers in the glaze are realized.
In the reaction process, because the zirconium-containing frit particles and the added zirconia and zircon sand are in a nano-scale mixed state, the added zirconia and zircon sand have sufficient opportunity to react with Ca, Mg, Zn and Sr in the frit to form zirconium-containing silicic acid M. When the zirconium in the frit meets the added zirconia, there is an opportunity to precipitate the zirconia. The added zirconium silicate also has the opportunity to meet the zirconium silicate precipitated from the clinker and grow gradually. Thus, three grains of zirconia grains, zirconium silicate grains, and zirconium-containing M-silicate grains coexist in the glaze.
As one preferred embodiment of the zirconium-containing frit, the composition of the zirconium-containing frit comprises: SiO 2 2 50.00~60.00%，Al 2 O 3 9.50~20.00%，CaO+MgO+SrO+ZnO=18.00~30.00%，K 2 O+Na 2 O=6.00~10.00%，ZrO 2 3.50~5.50%。
The preparation method of the slurry of the nano soft super wear-resistant diamond glaze comprises the following steps:
(1) uniformly mixing raw materials containing zirconium frits, adding the raw materials into a frit furnace to be melted into molten glass, and then pouring the molten glass into water to be quenched to obtain the zirconium-containing frits;
preferably, the raw material of the zirconium-containing frit is one or more of quartz, potash feldspar, albite, talc, wollastonite, dolomite, calcite, zinc oxide, strontium carbonate, alumina, zirconium silicate and zirconium oxide.
Preferably, the melting temperature of the frit furnace is 1450-1650 ℃.
(2) According to the chemical composition of the nano soft super wear-resistant diamond glaze, adding zirconium-containing frit, zirconium silicate, zirconium oxide, kaolin and an auxiliary agent into a ball mill, and carrying out ball milling to obtain glaze slurry;
the selection range of the addition amounts of the zirconium-containing frit, zirconium silicate, zirconium oxide, kaolin, and the auxiliary agent is set with reference to the raw materials of the nano soft super wear-resistant diamond glaze described above.
(3) And (3) carrying out nano grinding on the glaze slip to obtain the nano glaze slip with the average grain diameter controlled less than 900 nm.
Preferably, the glaze slip is subjected to nano grinding to obtain the nano glaze slip with the average particle size controlled to be 500-800 nm.
And (3) carrying out nano grinding on the glaze slip to enable the zirconium-containing frit particles and the added zirconia and zircon sand to be in a nano-scale mixed state in the reaction process, so that after the nano soft-light super-wear-resistant diamond glaze slip is fired, the added zirconia and zircon sand have sufficient opportunity to react with Ca, Mg, Zn and Sr in the frit to form zirconium-containing silicic acid M. When the zirconium in the frit meets the added zirconia, there is an opportunity to precipitate the zirconia. The added zirconium silicate also has the opportunity to meet the zirconium silicate precipitated from the clinker and grow gradually. Thus, three kinds of grains of zirconia grains, zirconium silicate grains, and zirconium-containing M-silicate grains are coexistent in the glaze.
On the other hand, the invention also provides a nanometer subdued light super-wear-resistant ceramic tile which comprises a ceramic tile blank and a diamond glaze layer arranged on the ceramic tile blank, wherein the diamond glaze layer is made of the nanometer subdued light super-wear-resistant diamond glaze. The technical details of the nano soft super wear-resistant diamond glaze are the same as those described above, and are not described herein again.
Because the nano zirconia crystal grains, the zirconium silicate crystal grains and the zirconium-containing M crystal grains are coexisted in the diamond glaze, the formed glaze layer is very thin, visible light can more easily penetrate through the glaze layer, the glaze layer has enough transparency, a pattern layer below the glaze layer can be displayed truly, and the color development effect is good. Moreover, the invention has excellent hardness, wear resistance and antifouling performance simultaneously by enabling a sufficient number of high-hardness crystal grains (zirconium oxide, zirconium silicate and zirconium-containing silicic acid M) to be in the glaze and controlling the grain sizes of the zirconium oxide crystal grains, the zirconium silicate crystal grains and the zirconium-containing silicic acid M.
Preferably, the thickness of the diamond glaze layer is 10-15 microns, which is beneficial to ensuring that the glaze layer has ideal transparency, and the pattern layer below the glaze layer is displayed really.
Generally, a higher zirconium content in the glaze layer will result in a higher refractive index, which in turn will form an opacifying covering layer that will affect the color development of the tile. However, the present invention can avoid forming an opacifying covering layer and ensure a color-developing effect by controlling the thickness of the diamond glaze layer and the particle size of the coexisting crystal grains.
Preferably, the ceramic tile blank comprises the following chemical compositions in percentage by weight:
SiO 2 65~70%，Al 2 O 3 19~21%，CaO+MgO=0.35~0.8%，K 2 O+Na 2 o = 4.5-5.5%, and loss on ignition is 4.5-5.5%.
It should be noted that the diamond glaze of the present invention can be applied to a plurality of component bodies, and the above-mentioned bodies are only one preferred embodiment.
Preferably, the ceramic tile blank further comprises a ground coat coated on the ceramic tile blank, and the ground coat comprises the following chemical compositions in percentage by weight: SiO 2 2 60~65%，Al 2 O 3 22~25%，CaO+MgO=0.15~0.50%，K 2 O+Na 2 O=2.5~3.5%，ZnO 1.5~2.0%，ZrO 2 6-9% and 2.5-3.3% of loss on ignition, the content of calcium, magnesium and zinc is reduced by controlling the chemical composition of the ground glaze, the content of potassium and sodium is controlled to be 2.5-3.5%, and if the content of potassium, sodium, calcium, magnesium and zinc is too low, the ground glaze is burnt, so that a firm blank glaze bonding layer is not formed, and the color development is not good. If the content of calcium, magnesium and zinc is too high, excessive and coarse zirconium-containing M crystal grains of silicic acid tend to be formed, resulting in poor transparency and color development of the glaze.
It should be noted that the present invention is applicable to ground enamels of other formulations than the preferred ground enamel described above.
In another aspect, as shown in fig. 1, the present invention further provides a method for preparing a nano soft super wear-resistant diamond-glazed ceramic tile, comprising:
s101, selecting/preparing a ceramic tile blank;
preferably, step S101 includes:
according to the chemical component proportion of the ceramic tile blank, ball-milling the ceramic tile blank raw material and the blank auxiliary agent in a ball mill into slurry, and then sieving, deironing and spray-drying the slurry to obtain blank powder with the water content of 5.5-7.5%;
pressing the mixture into blank powder by a press to obtain a wet blank;
and drying the wet blank to obtain the ceramic tile blank.
The ceramic tile blank body is prepared from one or more of black mud, mixed mud, kaolin, high-temperature sand, feldspar, talc and bauxite;
the green body additive is one or more of a water reducing agent and a green body reinforcing agent.
The ceramic tile blank prepared in the step S101 comprises the following chemical components in percentage by weight: SiO 2 2 65~70%，Al 2 O 3 19~21%，CaO+MgO=0.35~0.8%，K 2 O+Na 2 O = 4.5-5.5%, and loss on ignition is 4.5-5.5%.
It should be noted that, other existing blanks may also be used in step S101, and the implementation manner is not limited to the illustrated embodiment of the present invention.
S102, selecting/preparing a ground glaze;
preferably, step S102 includes:
according to the chemical component proportion of the ground glaze, ball-milling the ground glaze raw material and the ground glaze auxiliary agent into slurry in a ball mill to obtain the ground glaze;
wherein the ground glaze raw material is one or more of quartz, potassium feldspar, albite, talc, wollastonite, dolomite, calcite, zinc oxide, zirconium silicate and kaolin;
the ground glaze auxiliary agent is one or more of a water reducing agent and methyl cellulose.
The ground glaze prepared in the step S102 comprises the following chemical components in percentage by weight: SiO 2 2 60~65%，Al 2 O 3 22~25%，CaO+MgO=0.15~0.50%，K 2 O+Na 2 O=2.5~3.5%，ZnO 1.5~2.0%，ZrO 2 6 to 9 percent, and the ignition loss is 2.5 to 3.3 percent
It should be noted that, other existing ground enamels may also be used in step S102, and the implementation manner is not limited to the illustrated embodiment of the present invention.
S103, preparing nano soft super wear-resistant diamond glaze;
preferably, step S103 includes:
uniformly mixing raw materials containing zirconium frits, adding the raw materials into a frit furnace to be melted into molten glass, and then pouring the molten glass into water to be quenched to obtain the zirconium-containing frits;
adding the raw materials of the nanometer soft super wear-resistant diamond glaze into a ball mill according to the chemical composition of the nanometer soft super wear-resistant diamond glaze, and carrying out ball milling to obtain glaze slurry;
and grinding the glaze slip to obtain the nano glaze slip with the average grain diameter controlled less than 900 nanometers.
Wherein, the nano soft super wear-resistant diamond glaze is prepared from zirconium-containing frit, zirconium silicate, zirconium oxide, kaolin and an auxiliary agent;
the raw materials of the zirconium-containing frit are selected from one or more of quartz, potassium feldspar, albite, talc, wollastonite, dolomite, calcite, zinc oxide, strontium carbonate, alumina, zirconium silicate and zirconium oxide.
Preferably, the nano soft super wear-resistant diamond glaze prepared in step S103 comprises the following chemical compositions in percentage by weight: SiO 2 2 50.00~59.00%，Al 2 O 3 11.00~26.00%，CaO+MgO+SrO+ZnO=12.00~31.00%，K 2 O+Na 2 O=5.00~9.30%，ZrO 2 3.00-6.50% and 0.70-2.01% of loss on ignition. The technical details of the nano soft super wear-resistant diamond glaze are the same as those described above, and are not repeated herein.
S104, applying the ground glaze on the ceramic tile blank, and performing ink-jet printing on a pattern;
in step S104, the ground glaze is applied to the tile blank, and then the inkjet printing pattern or the non-inkjet printing pattern can be selected.
And S105, applying the nano soft super wear-resistant diamond glaze on the ground coat to obtain a diamond glaze layer, drying, and firing in a kiln.
In the step S105, preferably, the firing period is 30-180 minutes, the maximum firing temperature is 1190-1220 ℃, and the heat preservation time of the maximum firing temperature is 5-20 minutes; the time required for cooling from the highest firing temperature to 950-1050 ℃ is 15-35 minutes, and the coexisting zirconium oxide crystal grains with the grain size of 500-800 nanometers, zirconium silicate crystal grains with the grain size of 1-3 micrometers and zirconium-containing silicate M crystal grains with the grain size of 3-6 micrometers in the glaze are realized.
Wherein the highest firing temperature is set to 1190-1220 ℃, the glaze is just as fired, and the blank glaze is just suitable. When the firing temperature is higher than 1220 ℃, on one hand, the blank body is over-fired and expanded to cause the blank glaze to be not suitable, and bubbles generated by over-firing of the blank body cause a glaze surface to generate a large amount of glaze bubbles; meanwhile, zirconium silicate and zirconium oxide which serve as crystal nuclei in the glaze are dissolved or partially dissolved, so that the crystal grains are difficult to precipitate, and the hardness and the wear resistance of the glaze are poor. When the firing temperature is less than 1190 ℃, on one hand, the intermediate layer of the green glaze is difficult to form due to green firing of the green body; meanwhile, the glaze is burnt, and the raw burning of the glaze shows that bubbles in the glaze are not completely eliminated, the transparency of the glaze is poor and the like, so that the quality of the glaze surface is influenced.
The cooling of the maximum firing temperature to 950-1050 ℃ requires 15-35 minutes, and 950-1050 ℃ is the temperature range of the common nucleation and growth of three crystal grains of zirconium oxide, zirconium silicate and zirconium-containing silicic acid M in the glaze of the system. When the temperature range time is less than 15 minutes, three kinds of crystal grains of zirconia, zirconium silicate and zirconium-containing silicic acid M are less nucleated, and finally the number of the three kinds of crystal grains tends to be too small. The hardness and wear resistance of the glaze surface are difficult to reach ideal values. When the temperature range is longer than 35 minutes, the zirconia, the zirconium silicate and the zirconium-containing silicic acid M are easy to nucleate too much, the crystal grains are easy to be too large, the opacity of the glaze is increased, and the transparency is reduced. Meanwhile, the temperature range of the section is more than 35 minutes, the yield per unit time is reduced, the energy consumption is increased, and the cost is increased.
Preferably, the firing period is 50-150 minutes, the maximum firing temperature is 1200-1210 ℃, and the heat preservation time of the maximum firing temperature is 10-15 minutes; the time required for cooling from the maximum firing temperature to 980 ℃ to 1020 ℃ is 20 to 30 minutes.
In the reaction process, because the zirconium-containing frit particles and the added zirconia and zircon sand are in a nano-scale mixed state, the added zirconia and zircon sand have sufficient opportunity to react with Ca, Mg, Zn and Sr in the frit to form zirconium-containing silicic acid M. When the zirconium in the frit meets the added zirconia, there is an opportunity to precipitate the zirconia. The added zirconium silicate also has the opportunity to meet the zirconium silicate precipitated from the clinker and grow gradually. Thus, three kinds of grains of zirconia grains, zirconium silicate grains, and zirconium-containing M-silicate grains are coexistent in the glaze.
Preferably, the thickness of the diamond glaze layer formed by sintering is 10-15 microns, which is beneficial to ensuring that the glaze layer has ideal transparency and the pattern layer below the glaze layer is displayed really.
Generally, a higher zirconium content in the glaze layer will result in a higher refractive index, which in turn will form an opacifying covering layer that affects the color development of the tile. However, the present invention can avoid the formation of an opacifying layer and ensure a color-developing effect by controlling the thickness of the diamond glaze layer and the particle size of the coexisting crystal grains.
In the invention, after the ground coat, the ink-jet printing pattern and the nano soft super wear-resistant diamond glaze are sequentially applied on the green body layer, the pattern layer can be further ink-jet printed, and the overglaze can be applied to form the overglaze layer.
And S105, after the ceramic tile is placed into a kiln to be sintered, edging the sintered semi-finished product to obtain a finished product of the nano soft super wear-resistant diamond glaze ceramic tile.
The invention is further illustrated by the following specific examples
Example 1
A. Selecting a ceramic tile blank;
B. selecting a base glaze;
C. preparing nano soft super wear-resistant diamond glaze, which comprises the following steps:
uniformly mixing raw materials containing zirconium frits, adding the raw materials into a frit furnace to be melted into molten glass, and then pouring the molten glass into water to be quenched to obtain the zirconium-containing frits;
according to the chemical composition of the nano soft super wear-resistant diamond glaze, 88.5kg of zirconium-containing frit, 10 kg of kaolin, 1 kg of zirconium silicate, 0.5 kg of zirconium oxide, 0.5 kg of water reducing agent and 0.1 kg of methyl cellulose are added into a ball mill for ball milling to obtain glaze slurry;
carrying out nano grinding on the glaze slip to obtain nano soft super wear-resistant diamond glaze with the average particle size controlled to be 500-800 nm;
D. applying the base glaze on the ceramic tile blank, and carrying out ink-jet printing on patterns;
E. and (3) applying the nano soft super wear-resistant diamond glaze on the ground glaze, controlling the thickness to be 10 microns, drying, and sintering in a kiln. The firing conditions were: the sintering period is 55 minutes, the maximum sintering temperature is 1220 ℃, and the heat preservation time of the maximum sintering temperature is 6 minutes; the time required for cooling from the maximum firing temperature to 1050 ℃ was 22 minutes.
After sintering, the nano soft super wear-resistant diamond glaze comprises the following chemical compositions in percentage by weight:
SiO 2 50.14%，Al 2 O 3 15.52%，CaO+MgO+SrO+ZnO=20.2%，K 2 O+Na 2 O=7.75%，ZrO 2 5.11%，SiO 2 /Al 2 O 3 =3.2，K 2 O/Na 2 o =1.1, loss on ignition 1.28%.
Zirconia crystal grains with the grain diameter of 500-800 nanometers, zirconium silicate crystal grains with the grain diameter of 1-3 micrometers and zirconium-containing silicic acid M crystal grains with the grain diameter of 3-6 micrometers coexist in the glaze slip, wherein M represents any one or combination of calcium, magnesium, strontium and zinc.
Example 2
A. Selecting a ceramic tile blank;
B. selecting a base glaze;
C. preparing nano soft super wear-resistant diamond glaze, which comprises the following steps:
uniformly mixing raw materials containing zirconium frits, adding the raw materials into a frit furnace to be melted into molten glass, and then pouring the molten glass into water to be quenched to obtain the zirconium-containing frits;
according to the chemical composition of the nano soft super wear-resistant diamond glaze, 89.5kg of zirconium-containing frit, 9 kg of kaolin, 0.5 kg of zirconium silicate, 1 kg of zirconia, 0.5 kg of water reducing agent and 0.1 kg of methyl cellulose are added into a ball mill for ball milling to obtain glaze slurry;
carrying out nano grinding on the glaze slip to obtain nano soft super wear-resistant diamond glaze with the average particle size controlled to be 500-800 nm;
D. applying the base glaze on the ceramic tile blank, and carrying out ink-jet printing on patterns;
E. and (3) applying the nano soft super wear-resistant diamond glaze on the ground glaze, controlling the thickness to be 12 microns, drying, and firing in a kiln. The firing conditions were: the firing period is 65 minutes, the maximum firing temperature is 1210 ℃, and the heat preservation time of the maximum firing temperature is 8 minutes; the time required for cooling from the maximum firing temperature to 1000 c was 25 minutes.
After sintering, the nano soft super wear-resistant diamond glaze comprises the following chemical compositions in percentage by weight:
SiO 2 55.08%，Al 2 O 3 12.35%，CaO+MgO+SrO+ZnO=20.46%，K 2 O+Na 2 O=5.31%，ZrO 2 5.25%，SiO 2 /Al 2 O 3 =4.5，K 2 O/Na 2 o =1.5, loss on ignition 1.55%.
Zirconia crystal grains with the grain diameter of 500-800 nanometers, zirconium silicate crystal grains with the grain diameter of 1-3 micrometers and zirconium-containing silicic acid M crystal grains with the grain diameter of 3-6 micrometers coexist in the glaze slip, wherein M represents any one or the combination of calcium, magnesium, strontium and zinc.
Example 3
A. Selecting a ceramic tile blank;
B. selecting a base glaze;
C. preparing nano soft super wear-resistant diamond glaze, which comprises the following steps:
uniformly mixing raw materials containing zirconium frits, adding the raw materials into a frit furnace to be melted into molten glass, and then pouring the molten glass into water to be quenched to obtain the zirconium-containing frits;
adding 92.5kg of zirconium-containing frit, 6kg of kaolin, 1 kg of zirconium silicate, 0.5 kg of zirconium oxide, 0.5 kg of water reducing agent and 0.1 kg of methyl cellulose into a ball mill according to the chemical composition of the nano soft super wear-resistant diamond glaze, and carrying out ball milling to obtain glaze slurry;
carrying out nano grinding on the glaze slip to obtain nano soft super wear-resistant diamond glaze with the average particle size controlled to be 500-800 nm;
D. applying the base glaze on the ceramic tile blank, and carrying out ink-jet printing on patterns;
E. and (3) applying the nano soft super wear-resistant diamond glaze on the ground glaze, controlling the thickness to be 15 microns, drying, and sintering in a kiln. The firing conditions were: the firing period is 75 minutes, the maximum firing temperature is 1215 ℃, and the heat preservation time of the maximum firing temperature is 10 minutes; the time required for cooling from the maximum firing temperature to 950 ℃ was 28 minutes.
The nano soft super wear-resistant diamond glaze comprises the following chemical components in percentage by weight:
SiO 2 52.43%，Al 2 O 3 20.41%，CaO+MgO+SrO+ZnO=15.93%，K 2 O+Na 2 O=5.31%，ZrO 2 5.04%，SiO 2 /Al 2 O 3 =2.6，K 2 O/Na 2 o =2.5, loss on ignition 0.88%.
Zirconia crystal grains with the grain diameter of 500-800 nanometers, zirconium silicate crystal grains with the grain diameter of 1-3 micrometers and zirconium-containing silicic acid M crystal grains with the grain diameter of 3-6 micrometers coexist in the glaze slip, wherein M represents any one or combination of calcium, magnesium, strontium and zinc.
Example 4
A. Selecting a ceramic tile blank;
B. selecting a base glaze;
C. preparing nano soft super wear-resistant diamond glaze, which comprises the following steps:
uniformly mixing raw materials containing zirconium frits, adding the raw materials into a frit furnace to be melted into molten glass, and then pouring the molten glass into water to be quenched to obtain the zirconium-containing frits;
according to the chemical composition of the nano soft super wear-resistant diamond glaze, 86kg of zirconium-containing frit, 13 kg of kaolin, 0.5 kg of zirconium silicate, 0.5 kg of zirconium oxide, 0.5 kg of water reducing agent and 0.1 kg of methyl cellulose are added into a ball mill for ball milling to obtain glaze slurry;
nano-grinding the glaze slip to obtain nano soft super wear-resistant diamond glaze with the average particle size controlled to be 500-800 nm;
D. applying the base glaze on the ceramic tile blank, and carrying out ink-jet printing on patterns;
E. and (3) applying the nano soft super wear-resistant diamond glaze on the ground glaze, controlling the thickness to be 13 microns, drying, and sintering in a kiln. The firing conditions were: the firing period is 85 minutes, the maximum firing temperature is 1220 ℃, and the heat preservation time of the maximum firing temperature is 15 minutes; the time required for cooling from the maximum firing temperature to 980 ℃ was 30 minutes.
After sintering, the nano soft super wear-resistant diamond glaze comprises the following chemical compositions in percentage by weight:
SiO 2 59.00%，Al 2 O 3 13.18%，CaO+MgO+SrO+ZnO=16.88%，K 2 O+Na 2 O=6.14%，ZrO 2 3.56%，SiO 2 /Al 2 O 3 =4.47，K 2 O/Na 2 o =1.6, loss on ignition 1.24%.
Zirconia crystal grains with the grain diameter of 500-800 nanometers, zirconium silicate crystal grains with the grain diameter of 1-3 micrometers and zirconium-containing silicic acid M crystal grains with the grain diameter of 3-6 micrometers coexist in the glaze slip, wherein M represents any one or the combination of calcium, magnesium, strontium and zinc.
Example 5
A. Selecting a ceramic tile blank;
B. selecting a base glaze;
C. preparing nano soft super wear-resistant diamond glaze, which comprises the following steps:
uniformly mixing raw materials containing zirconium frits, adding the raw materials into a frit furnace to be melted into molten glass, and then pouring the molten glass into water to be quenched to obtain the zirconium-containing frits;
according to the chemical composition of the nanometer soft light super wear-resistant diamond glaze, 83kg of zirconium-containing frit, 15 kg of kaolin, 1 kg of zirconium silicate, 1 kg of zirconium oxide, 0.5 kg of water reducing agent and 0.1 kg of methyl cellulose are added into a ball mill for ball milling to obtain glaze slurry;
carrying out nano grinding on the glaze slip to obtain nano soft super wear-resistant diamond glaze with the average particle size controlled to be 500-800 nm;
D. applying the base glaze on the ceramic tile blank, and carrying out ink-jet printing on patterns;
E. and (3) applying the nano soft super wear-resistant diamond glaze on the ground glaze, controlling the thickness to be 11 microns, drying, and sintering in a kiln. The firing conditions were: the firing period is 120 minutes, the maximum firing temperature is 1200 ℃, and the heat preservation time of the maximum firing temperature is 15 minutes; the time required for cooling from the maximum firing temperature to 1000 c was 30 minutes.
After sintering, the nano soft super wear-resistant diamond glaze comprises the following chemical compositions in percentage by weight:
SiO 2 57.65%，Al 2 O 3 13.44%，CaO+MgO+SrO+ZnO=15.04%，K 2 O+Na 2 O=5.98%，ZrO 2 6.13%，SiO 2 /Al 2 O 3 =4.3，K 2 O/Na 2 o =2.4, loss on ignition 1.76%.
Zirconia crystal grains with the grain diameter of 500-800 nanometers, zirconium silicate crystal grains with the grain diameter of 1-3 micrometers and zirconium-containing silicic acid M crystal grains with the grain diameter of 3-6 micrometers coexist in the glaze slip, wherein M represents any one or the combination of calcium, magnesium, strontium and zinc.
The technical tests carried out on the tiles described in examples 1 to 5 gave the following results:
from the above, the glossiness of the embodiments 1 to 5 is controlled within 15 to 30 degrees, and a good soft light effect is obtained; the hardness is high, and the Mohs hardness can reach 7-8; the wear resistance is good, the wear resistance grade reaches 4 grades, and 10000-12000 revolutions are achieved; moreover, the antifouling property is good, and the invisible marks can be basically reached for 10 times by adopting a blue oily marking pen.
The abrasion resistance was measured according to GB/T3810.7.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (18)
1. A nanometer subdued light super wear-resistant diamond glaze is characterized by comprising the following chemical compositions in percentage by weight:
SiO 2 50.00~59.00%，Al 2 O 3 11.00~26.00%，K 2 O+Na 2 O=5.00~9.30%，CaO+MgO+SrO+ZnO=12.00~31.00%，ZrO 2 3.00~6.50%，SiO 2 /Al 2 O 3 =2.5~4.5，K 2 O/Na 2 o = 1.1-3.0, and the ignition loss is 0.70-2.01%;
the sum of all chemical compositions is 100 percent;
the diamond glaze coexists with nano-zirconia grains, zirconium silicate grains and zirconium-containing silicic acid M grains, wherein M represents any one or combination of calcium, magnesium, strontium and zinc;
the grain size of the nanometer zirconia crystal grain is 300-900 nanometers, the grain size of the zirconium silicate crystal grain is 1-5 micrometers, and the grain size of the zirconium-containing silicic acid M crystal grain is 1-10 micrometers.
2. The nano soft super wear-resistant diamond glaze according to claim 1, wherein the nano zirconia crystal grains have a particle size of 500 to 800 nm, the zirconium silicate crystal grains have a particle size of 1 to 3 μ M, and the zirconium-containing M silicate crystal grains have a particle size of 3 to 6 μ M.
3. The nano subdued light super wear-resistant diamond glaze as set forth in claim 1, wherein the nano subdued light super wear-resistant diamond glaze has a glossiness of 15 to 30 degrees.
4. The nano soft super wear-resistant diamond glaze according to claim 1, wherein the nano soft super wear-resistant diamond glaze mainly comprises the following raw materials in parts by weight:
80-95 parts of zirconium-containing frit, 0.1-10 parts of zirconium silicate, 0.1-10 parts of zirconium oxide, 1-20 parts of kaolin and 0.1-5 parts of auxiliary agent.
5. The nano soft super abrasive diamond glaze according to claim 4, wherein the chemical composition of said zirconium-containing frit comprises: SiO 2 2 50.00~60.00%，Al 2 O 3 9.50~20.00%，CaO+MgO+SrO+ZnO=18.00~30.00%，K 2 O+Na 2 O=6.00~10.00%，ZrO 2 3.50~5.50%。
6. The nano soft super abrasive diamond glaze according to claim 1 or 4, wherein said nano soft super abrasive diamond glaze is fired under the following conditions: the firing period is 30-180 minutes; the highest firing temperature is 1190-1220 ℃, and the heat preservation time of the highest firing temperature is 5-20 minutes;
the time required for cooling from the maximum firing temperature to 950-1050 ℃ is 15-35 minutes.
7. A nano soft super wear-resistant ceramic tile, which comprises a ceramic tile blank and a diamond glaze layer arranged on the ceramic tile blank, wherein the diamond glaze layer is made of the nano soft super wear-resistant diamond glaze according to any one of claims 1 to 6.
8. The nano soft super wear-resistant ceramic tile according to claim 7, wherein the thickness of the diamond glaze layer is 10-15 μm.
9. The nano soft super wear-resistant tile according to claim 7, wherein the tile blank comprises the following chemical components in percentage by weight:
SiO 2 65~70%，Al 2 O 3 19~21%，CaO+MgO=0.35~0.8%，K 2 O+Na 2 o = 4.5-5.5%, and loss on ignition is 4.5-5.5%.
10. The nano soft light super wear-resistant ceramic tile according to claim 7, further comprising a ground glaze coated on the tile blank, wherein the ground glaze comprises the following chemical compositions in percentage by weight:
SiO 2 60~65%，Al 2 O 3 22~25%，CaO+MgO=0.15~0.50%，K 2 O+Na 2 O=2.5~3.5%，ZnO 1.5~2.0%，ZrO 2 6-9% and 2.5-3.3% of loss on ignition.
11. A preparation method of a nanometer soft-light super wear-resistant diamond glaze ceramic tile is characterized by comprising the following steps:
A. selecting/preparing a ceramic tile blank;
B. selecting/preparing base glaze;
C. preparing a slurry of nano soft super abrasion resistant diamond glaze according to any one of claims 1 to 6;
D. applying the base glaze on the ceramic tile blank, and carrying out ink-jet printing on patterns;
E. and (3) applying the nano soft super wear-resistant diamond glaze on the ground coat to obtain a diamond glaze layer, drying and firing in a kiln.
12. The method for preparing a nano subdued light super wear resistant diamond-glazed ceramic tile as claimed in claim 11 wherein step C comprises:
uniformly mixing raw materials containing zirconium frits, adding the raw materials into a frit furnace to be melted into molten glass, and then pouring the molten glass into water to be quenched to obtain the zirconium-containing frits;
the chemical composition of the nano soft super wear-resistant diamond glaze according to any one of claims 1 to 6, wherein the raw material of the nano soft super wear-resistant diamond glaze is added into a ball mill for ball milling to obtain glaze slip;
and grinding the glaze slip to obtain the nano glaze slip with the average grain diameter controlled to be less than 900 nanometers.
13. The method for preparing a nano soft ultra wear-resistant diamond-glazed ceramic tile according to claim 12, wherein the nano soft ultra wear-resistant diamond glaze is prepared from a zirconium-containing frit, zirconium silicate, zirconium oxide, kaolin and an auxiliary agent.
14. The method for preparing a nano subdued light super wear-resistant diamond-glazed ceramic tile as claimed in claim 11, wherein in the step E, the firing period is 30-180 minutes;
the maximum firing temperature is 1190-1220 ℃, and the heat preservation time of the maximum firing temperature is 5-20 minutes;
the time required for cooling from the maximum firing temperature to 950-1050 ℃ is 15-35 minutes.
15. The method for preparing a nano soft super wear-resistant diamond-glazed ceramic tile according to claim 11 or 14, wherein in the step E, the thickness of the diamond glaze layer is 10-15 μm.
16. The method for preparing a nano soft super wear-resistant diamond-glazed ceramic tile according to claim 11, wherein the step a comprises:
according to the chemical component proportion of the ceramic tile blank, ball-milling the ceramic tile blank raw material and the blank auxiliary agent in a ball mill into slurry, and then sieving, deironing and spray-drying the slurry to obtain blank powder with the water content of 5.5-7.5%;
pressing the mixture into blank powder by a press to obtain a wet blank;
and drying the wet blank to obtain the ceramic tile blank.
17. The method for preparing a nano subdued light super wear-resistant diamond-glazed ceramic tile as claimed in claim 16, wherein the green body assistant is one or more of a water reducing agent and a green body reinforcing agent.
18. The method for preparing a nano soft super wear-resistant diamond-glazed ceramic tile according to claim 11, wherein the step B comprises:
according to the chemical component proportion of the ground glaze, ball-milling the ground glaze raw material and the ground glaze auxiliary agent into slurry in a ball mill to obtain the ground glaze;
wherein the ground glaze auxiliary agent is one or more of a water reducing agent and methyl cellulose.
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Application publication date: 20220722 Assignee: Foshan dajiaolu marble tile Co.,Ltd. Assignor: Guangdong dajiaolu New Material Co.,Ltd. Contract record no.: X2024980000565 Denomination of invention: A nano soft light ultra wear-resistant diamond glaze, ceramic tile and its preparation method Granted publication date: 20220930 License type: Common License Record date: 20240112 |
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Application publication date: 20220722 Assignee: Foshan dajiaolu marble tile Co.,Ltd. Assignor: Guangdong dajiaolu New Material Co.,Ltd. Contract record no.: X2024980000565 Denomination of invention: A nano soft light ultra wear-resistant diamond glaze, ceramic tile and its preparation method Granted publication date: 20220930 License type: Common License Record date: 20240112 |