CN113929306B - Photocatalyst antibacterial ceramic glaze, preparation method thereof and light ceramic tile - Google Patents
Photocatalyst antibacterial ceramic glaze, preparation method thereof and light ceramic tile Download PDFInfo
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- CN113929306B CN113929306B CN202111279682.0A CN202111279682A CN113929306B CN 113929306 B CN113929306 B CN 113929306B CN 202111279682 A CN202111279682 A CN 202111279682A CN 113929306 B CN113929306 B CN 113929306B
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- photocatalyst
- glaze
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- ceramic glaze
- antibacterial ceramic
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 180
- 239000000919 ceramic Substances 0.000 title claims abstract description 108
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title abstract description 23
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 50
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002131 composite material Substances 0.000 claims abstract description 34
- 239000011787 zinc oxide Substances 0.000 claims abstract description 25
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 18
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 11
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims description 31
- 229910052708 sodium Inorganic materials 0.000 claims description 23
- 239000011734 sodium Substances 0.000 claims description 23
- 239000006185 dispersion Substances 0.000 claims description 20
- 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 claims description 18
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 18
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 18
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 18
- 239000002689 soil Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 17
- 238000000227 grinding Methods 0.000 claims description 11
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 230000000845 anti-microbial effect Effects 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 10
- 238000003837 high-temperature calcination Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 3
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 2
- 230000004298 light response Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 59
- 230000000052 comparative effect Effects 0.000 description 30
- 239000000203 mixture Substances 0.000 description 13
- 239000005995 Aluminium silicate Substances 0.000 description 10
- 235000012211 aluminium silicate Nutrition 0.000 description 10
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 10
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000005245 sintering Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000000498 ball milling Methods 0.000 description 6
- 238000005034 decoration Methods 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910021532 Calcite 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
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000000454 talc Substances 0.000 description 5
- 235000012222 talc Nutrition 0.000 description 5
- 229910052623 talc Inorganic materials 0.000 description 5
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 5
- 238000000748 compression moulding Methods 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 4
- 229910010271 silicon carbide Inorganic materials 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- MQWCQFCZUNBTCM-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(SC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O MQWCQFCZUNBTCM-UHFFFAOYSA-N 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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
-
- 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
-
- 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
- C03C2204/00—Glasses, glazes or enamels with special properties
- C03C2204/02—Antibacterial glass, glaze or enamel
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
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- C—CHEMISTRY; METALLURGY
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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
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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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
- 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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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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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
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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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
- C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3272—Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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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
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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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
- C04B2235/9646—Optical properties
- C04B2235/9653—Translucent or transparent ceramics other than alumina
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
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- Geochemistry & Mineralogy (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of antibacterial ceramic materials, and particularly discloses a photocatalyst antibacterial ceramic glaze, a preparation method thereof and a lightweight ceramic tile. The photocatalyst antibacterial ceramic glaze contains a composite photocatalyst, wherein the composite photocatalyst comprises a first photocatalyst and a second photocatalyst, and the first photocatalyst wraps the second photocatalyst; the first photocatalyst comprises titanium dioxide; the second photocatalyst comprises at least one of zinc oxide, silicon nitride and tin dioxide. The invention wraps the high Wen Zhongyi oxidized and lost second photocatalyst by using the first catalyst with higher chemical stability so as to effectively maintain the photocatalytic performance of the second photocatalyst; the first photocatalyst and the second photocatalyst form heterojunction in the high-temperature calcination process, the light response range of the first photocatalyst is expanded from an ultraviolet light region to a visible light region, the application range of the antibacterial ceramic glaze is greatly expanded, and meanwhile, the antibacterial effect is enhanced.
Description
Technical Field
The invention belongs to the technical field of antibacterial ceramic materials, and particularly relates to a photocatalyst antibacterial ceramic glaze, a preparation method thereof and a light ceramic tile.
Background
The photocatalyst is a generic name of a class of photo-semiconductor materials with a photocatalysis function, and is one of materials for treating environmental pollution. The photocatalyst can produce photocatalytic reaction similar to photosynthesis under the irradiation of light, generates free hydroxyl and active oxygen with extremely strong oxidizing capability, has extremely strong photooxidation-reduction function, can oxidize and decompose various organic compounds and partial inorganic matters, can destroy bacterial membranes and solidify proteins of viruses, can kill bacteria and decompose organic pollutants, and can decompose the organic pollutants into pollution-free water and carbon dioxide, so that the photocatalyst has extremely strong functions of sterilization, deodorization, mildew prevention, antifouling self-cleaning and air purification.
At present, photo-semiconductor materials with photocatalysis, namely photo-catalysts, can be divided into two types according to high temperature resistance: the first type is a high temperature resistant photocatalyst represented by nano titanium dioxide; the other class is a photocatalyst which is not resistant to high temperatures. When the two types of photocatalysts are applied to ceramic products, the ceramic products are all required to be sintered at high temperature, and the nanometer titanium dioxide is easy to generate crystal form transformation at high temperature, so that the photoresponse range of the photocatalyst is narrowed, and the photocatalyst can only play an antibacterial effect when being irradiated by ultraviolet light; photocatalysts that are not resistant to high temperatures are susceptible to oxidation at high temperatures and to loss during calcination. Therefore, the application of the existing photocatalyst to ceramic products is limited to a certain extent, and the existing photocatalyst cannot exert a good antibacterial effect. In addition, part of the photocatalyst has a certain color, and when the photocatalyst is applied to ceramic glaze, the decoration effect is affected, so that the application range of the photocatalyst is limited.
Therefore, it is needed to develop a photocatalyst antibacterial ceramic glaze, which can maintain good antibacterial function after high-temperature calcination and does not affect the decoration effect of the glaze.
Disclosure of Invention
The invention provides a photocatalyst antibacterial ceramic glaze, a preparation method thereof and a light ceramic tile, 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 overcome the technical problems, the first technical scheme of the invention is to provide a photocatalyst antibacterial ceramic glaze.
Specifically, the photocatalyst antibacterial ceramic glaze contains a composite photocatalyst, wherein the composite photocatalyst comprises a first photocatalyst and a second photocatalyst, and the first photocatalyst wraps the second photocatalyst;
the first photocatalyst comprises titanium dioxide; the second photocatalyst comprises at least one of zinc oxide, silicon nitride and tin dioxide.
According to the invention, the composite photocatalyst is added into the ceramic glaze, and comprises a first photocatalyst and a second photocatalyst, wherein the composite photocatalyst has a core-shell structure, the first photocatalyst is a shell, the second photocatalyst is a core, and the first photocatalyst wraps the second photocatalyst. Wherein: when the first photocatalyst titanium dioxide is calcined to be more than 900 ℃, the anatase crystal form is converted into the rutile crystal form, although the chemical stability of the rutile titanium dioxide is higher, the light response range is narrowed, the photocatalysis response cannot be carried out in the visible light region, only when the ultraviolet radiation is carried out, electron-hole pairs, namely photo-generated carriers, are generated by excitation due to the absorption of light energy in the titanium dioxide, then the photo-generated carriers rapidly migrate to the surface of the titanium dioxide and activate adsorbed oxygen and moisture to generate active free hydroxyl (OH) and active oxygen (O), and when pollutants and bacteria adsorb the surface of the titanium dioxide, chain degradation reaction can occur to achieve the sterilization effect; the second photocatalyst, zinc oxide, silicon nitride, tin dioxide, oxidizes and wears away at a height Wen Zhongyi. According to the invention, the first photocatalyst with higher chemical stability is used for wrapping the second photocatalyst with high Wen Zhongyi oxidation and loss, so that on one hand, the photocatalytic performance of the second photocatalyst can be effectively maintained, and on the other hand, the first photocatalyst and the second photocatalyst form a heterojunction in the high-temperature calcination process, so that the photoresponse range of the first photocatalyst is expanded from an ultraviolet light region to a visible light region, and the application range of the antibacterial ceramic glaze is greatly widened. Meanwhile, the first photocatalyst and the second photocatalyst act together, so that the photocatalytic performance of the ceramic glaze can be greatly improved, and the antibacterial effect is further enhanced.
As a further improvement of the above-mentioned scheme, the particle diameter of the second photocatalyst is 5 to 30nm.
Specifically, by controlling the particle diameter of the second photocatalyst to be in a suitable range, it is advantageous to expand the photoresponse range of the second photocatalyst so as to be maintained within the visible light region. The overlarge grain size can reduce the photocatalysis effect and the photoresponse range; if the particle size is too small, agglomeration is easy to occur, and false particles exist, so that the photocatalytic effect and the photoresponse range are also affected. Meanwhile, the second photocatalyst with the particle size range has transparent characteristics and does not influence the glaze decoration effect of the ceramic glaze.
As a further improvement of the scheme, the photocatalyst antibacterial ceramic glaze also contains at least one of transparent frit powder, water-washed soil, sodium hydroxymethyl cellulose and sodium tripolyphosphate.
Specifically, transparent frit is added into the photocatalyst antibacterial ceramic glaze, so that the glaze decoration effect of the glaze is guaranteed; the water-washed soil is used as a main source of mullite in the glaze, so that the glaze is endowed with good mechanical property and chemical stability; the sodium hydroxymethyl cellulose is used as a dispersing agent of the glaze, is mainly used as a binder in the glaze slurry, plays a suspension role at the same time, is beneficial to dispersing the glaze slurry, improves the fluidity of the glaze slurry, and increases the smoothness of the glaze surface; the sodium tripolyphosphate is used as a dispergator, so that the fluidity of the glaze slip can be effectively improved, flocculation precipitation is prevented, and the thixotropic property of the glaze slip is improved. Therefore, the composite photocatalyst and the raw materials of the photocatalyst antibacterial ceramic glaze work together, so that the basic performance and the decoration effect of the ceramic glaze are not affected while the antibacterial performance of the glaze is ensured.
Preferably, the photocatalyst antibacterial ceramic glaze comprises the following components in parts by weight: 20-45 parts of composite photocatalyst, 25-35 parts of transparent frit powder, 3.5-5 parts of water-washed soil, 0.1-0.15 part of sodium hydroxymethyl cellulose and 0.15-0.2 part of sodium tripolyphosphate.
The second technical scheme of the invention is that a preparation method of the photocatalyst antibacterial ceramic glaze is provided.
Specifically, the preparation method of the photocatalyst antibacterial ceramic glaze comprises the following steps:
mixing the composite photocatalyst with other raw materials for preparing the photocatalyst antibacterial ceramic glaze to obtain the photocatalyst antibacterial ceramic glaze.
As a further improvement of the scheme, the preparation method of the photocatalyst antibacterial ceramic glaze comprises the following steps of:
(1) Dispersing the second photocatalyst in absolute ethanol to obtain a dispersion solution;
(2) Under the acidic condition, butyl titanate is dropwise added into the dispersion solution, heating and stirring are carried out, and the composite photocatalyst is obtained after washing and drying;
(3) And mixing and grinding the composite photocatalyst, transparent frit powder, water-washed soil, sodium hydroxymethyl cellulose and sodium tripolyphosphate to obtain the photocatalyst antibacterial ceramic glaze.
Specifically, dispersing a second photocatalyst in absolute ethyl alcohol to uniformly disperse second photocatalyst particles so as to obtain a dispersion solution; then adding an acid solution into the dispersion solution to make the dispersion solution acidic, dropwise adding butyl titanate into the dispersion solution, and under the conditions of stirring and heating, firstly hydrolyzing the butyl titanate to obtain titanium hydroxide sol, and dehydrating the titanium hydroxide to obtain titanium dioxide gel, wherein the specific chemical reaction equation is as follows:
Ti(O-C 4 H 9 ) 4 +4H 2 O→Ti(OH) 4 +4C 4 H 9 OH
Ti(OH) 4 +Ti(O-C 4 H 9 ) 4 →2TiO 2 +4C 4 H 9 OH
2Ti(OH) 4 →2TiO 2 +4H 2 O
meanwhile, the titanium dioxide gel takes the second photocatalyst as a core to wrap the surface of the titanium dioxide gel, so that a photocatalyst with a core-shell structure is formed; washing the photocatalyst to remove substances and impurities which do not completely react, and drying to obtain the composite photocatalyst; finally, mixing and grinding the composite photocatalyst and other raw materials for preparing the photocatalyst antibacterial ceramic glaze, and obtaining the photocatalyst antibacterial ceramic glaze.
As a further improvement of the above scheme, the mass ratio of the second photocatalyst to the butyl titanate is 1: (0.5-2).
Specifically, the mass ratio of the second photocatalyst to the butyl titanate is controlled to control the mass ratio of the first photocatalyst to the second photocatalyst, so that the comprehensive antibacterial performance of the ceramic glaze is improved.
Preferably, in the step (2), the heating temperature is 50-80 ℃, and the stirring speed is 1000-1500r/min.
Further preferably, the stirring time is 3 to 5 hours.
Preferably, in the step (2), the washing is performed by a centrifugal washing method.
Further preferably, the centrifugal washing has a centrifugal rotational speed of 10000-13500r/min.
Preferably, in step (2), the number of times of washing is 4 to 6.
The third technical scheme of the invention is to provide an application of the photocatalyst antibacterial ceramic glaze.
Specifically, the light ceramic tile comprises a green body layer, a ground coat layer and a surface coat layer, wherein the surface coat layer is formed by firing the photocatalyst antibacterial ceramic glaze.
As a further improvement of the scheme, the raw material chemical composition of the green body layer comprises the following components in percentage by weight: siO (SiO) 2 55-60％、Al 2 O 3 15-20％、Fe 2 O 3 0.1-0.5％、CaO6-12％、MgO 1-5％、K 2 O 1-5％、Na 2 0.5-1% of O and 5-10% of burning loss. Specifically, the raw materials of the green body layer are the green body raw materials of the common light ceramic tile.
As a further improvement of the scheme, the glaze viscosity of the primer layer is 500-1000 Pa.s.
Preferably, the raw materials of the primer layer comprise the following components in parts by weight: 5-8 parts of potassium feldspar, 10-26 parts of calcite, 10-30 parts of barium carbonate, 2-5 parts of zirconium silicate, 3-8 parts of aluminum oxide, 2-5 parts of zinc oxide, 10-20 parts of calcined talcum, 3-10 parts of calcined kaolin, 5-8 parts of kaolin and 5-10 parts of quartz.
Specifically, the ignition loss of the raw materials of the green body of the lightweight ceramic tile is large, a large amount of bubbles are generated during high-temperature calcination, and the melt viscosity of the base glaze layer is controlled to be 500-1000 Pa.s by controlling the proportion of the raw materials in the base glaze layer, so that the bubbles generated by the green body layer are prevented from overflowing from the surface glaze layer through the base glaze layer, a large amount of pinholes are left in the surface glaze layer, and the glaze quality is influenced.
Preferably, the preparation method of the lightweight ceramic tile comprises the following steps:
(1) Grinding the raw materials of the green body layer, performing spray drying granulation, and performing compression molding to obtain the green body layer;
(2) Taking raw materials of a ground glaze layer and a surface glaze layer, and respectively grinding to obtain ground glaze slip and surface glaze slip;
(3) And (3) sequentially spraying the ground glaze slip and the surface glaze slip prepared in the step (2) on the surface of the green body layer prepared in the step (1), and sintering to prepare the light ceramic tile.
More preferably, in the step (3), the firing temperature is 1000-1300 ℃, and the firing period is 70-90 minutes.
The fourth technical scheme of the invention is to provide another application of the photocatalyst antibacterial ceramic glaze.
In particular to application of the photocatalyst antibacterial ceramic glaze in the ceramic field.
The technical scheme provided by the embodiment of the application has at least the following technical effects or advantages:
according to the invention, the composite photocatalyst is added into the ceramic glaze, has a core-shell structure, and the first photocatalyst with higher chemical stability is used for wrapping the second photocatalyst with high Wen Zhongyi oxidation and loss, so that the photocatalytic performance of the second photocatalyst is effectively maintained.
According to the invention, the first photocatalyst titanium dioxide, the second photocatalyst zinc oxide, the silicon nitride and the tin dioxide form a heterojunction in the high-temperature calcination process, so that the photoresponse range of the first photocatalyst is expanded from an ultraviolet light region to a visible light region, and the application range of the antibacterial ceramic glaze is greatly expanded. And the first photocatalyst and the second photocatalyst act together, so that the photocatalytic performance of the ceramic glaze can be greatly improved, and the antibacterial effect is further enhanced.
Detailed Description
The present invention is specifically described below by way of examples to facilitate the understanding of the present invention by those skilled in the art, and it is necessary to specifically point out that the examples are provided for further illustration only and are not to be construed as limiting the scope of the present invention, and that insubstantial modifications and adjustments of the present invention according to the above teachings should still fall within the scope of the present invention, and that the raw materials mentioned below are not specifically described, but are commercially available products, and that the process steps or preparation methods not specifically mentioned are those known to those skilled in the art.
Example 1
The photocatalyst antibacterial ceramic glaze comprises, by weight, 20 parts of a composite photocatalyst, 25 parts of transparent frit powder, 3.5 parts of water-washed soil, 0.1 part of sodium hydroxymethyl cellulose and 0.15 part of sodium tripolyphosphate. Wherein: the composite photocatalyst comprises titanium dioxide and zinc oxide, and the titanium dioxide wraps the zinc oxide; the particle size of the zinc oxide was 20nm.
The preparation method of the photocatalyst antibacterial ceramic glaze comprises the following steps:
(1) 100g of zinc oxide is placed in absolute ethyl alcohol to be stirred, and a dispersion solution is dispersed;
(2) Adding 2mol/L nitric acid into the dispersion solution prepared in the step (1), regulating the pH value of the dispersion solution to 5, dropwise adding 50g of butyl titanate into the dispersion solution, stirring at the speed of 1000r/min for 3 hours at the temperature of 50 ℃, centrifugally washing for 4 times, and drying to obtain a composite photocatalyst;
(3) Mixing the composite photocatalyst prepared in the step (2) with transparent frit powder, water-washed soil, sodium hydroxymethyl cellulose and sodium tripolyphosphate, and adding water for ball milling to prepare the photocatalyst antibacterial ceramic glaze of the embodiment.
A lightweight ceramic tile comprises a green body layer, a ground coat layer and a surface coat layer.
Wherein: the chemical composition of the raw materials of the green body layer comprises the following components in percentage by weight: siO (SiO) 2 58％、Al 2 O 3 15％、Fe 2 O 3 0.5％、CaO6％、MgO5％、K 2 O 5％、Na 2 0.5% of O and 10% of burning loss.
The raw materials of the ground coat layer comprise the following raw materials in parts by weight: 8 parts of potassium feldspar, 16 parts of calcite, 20 parts of barium carbonate, 5 parts of zirconium silicate, 8 parts of aluminum oxide, 5 parts of zinc oxide, 20 parts of calcined talcum, 5 parts of calcined kaolin, 8 parts of kaolin and 5 parts of quartz; the viscosity of the primer layer was 800 Pa.s.
The surface glaze layer adopts the photocatalyst antibacterial ceramic glaze material prepared by the embodiment.
The preparation method of the light ceramic tile comprises the following steps:
(1) Grinding the raw materials of the green body layer, performing spray drying granulation, and performing compression molding to obtain the green body layer;
(2) Grinding the ground glaze layer of the embodiment to obtain ground glaze slip;
(3) And (3) sequentially spraying the base glaze slip prepared in the step (2) and the photocatalyst antibacterial ceramic glaze prepared in the embodiment on the surface of the green body layer prepared in the step (1), and preparing the lightweight ceramic tile in the embodiment under the condition that the sintering temperature is 1180 ℃ and the sintering period is 70 minutes.
Example 2
The photocatalyst antibacterial ceramic glaze comprises, by weight, 30 parts of a composite photocatalyst, 30 parts of transparent frit powder, 4 parts of water-washed soil, 0.1 part of sodium hydroxymethyl cellulose and 0.15 part of sodium tripolyphosphate. Wherein: the composite photocatalyst comprises titanium dioxide and silicon carbide, and the titanium dioxide wraps the silicon carbide; the particle size of the silicon carbide was 15nm.
The preparation method of the photocatalyst antibacterial ceramic glaze comprises the following steps:
(1) 100g of silicon carbide is placed in absolute ethyl alcohol to be stirred, and a dispersion solution is dispersed;
(2) Adding 3.5mol/L nitric acid into the dispersion solution prepared in the step (1), regulating the pH value of the dispersion solution to 4, dropwise adding 100g of butyl titanate into the dispersion solution, stirring at the speed of 1200r/min for 3 hours at the temperature of 60 ℃, centrifuging and washing for 5 times, and drying to obtain a composite photocatalyst;
(3) Mixing the composite photocatalyst prepared in the step (2) with transparent frit powder, water-washed soil, sodium hydroxymethyl cellulose and sodium tripolyphosphate, and adding water for ball milling to prepare the photocatalyst antibacterial ceramic glaze of the embodiment.
A lightweight ceramic tile comprises a green body layer, a ground coat layer and a surface coat layer.
Wherein: the chemical composition of the raw materials of the green body layer comprises the following components in percentage by weight: siO (SiO) 2 56.7％、Al 2 O 3 16％、Fe 2 O 3 0.3％、CaO10％、MgO4％、K 2 O 4％、Na 2 O1% and 8% loss by burning.
The raw materials of the ground coat layer comprise the following raw materials in parts by weight: 5 parts of potassium feldspar, 16 parts of calcite, 23 parts of barium carbonate, 5 parts of zirconium silicate, 8 parts of aluminum oxide, 5 parts of zinc oxide, 20 parts of calcined talcum, 5 parts of calcined kaolin, 8 parts of kaolin and 5 parts of quartz; the viscosity of the primer layer was 900 Pa.s.
The surface glaze layer adopts the photocatalyst antibacterial ceramic glaze material prepared by the embodiment.
The preparation method of the light ceramic tile comprises the following steps:
(1) Grinding the raw materials of the green body layer, performing spray drying granulation, and performing compression molding to obtain the green body layer;
(2) Grinding the ground glaze layer of the embodiment to obtain ground glaze slip;
(3) And (3) sequentially spraying the base glaze slip prepared in the step (2) and the photocatalyst antibacterial ceramic glaze prepared in the embodiment on the surface of the green body layer prepared in the step (1), and preparing the lightweight ceramic tile in the embodiment under the condition that the sintering temperature is 1200 ℃ and the sintering period is 80 minutes.
Example 3
The photocatalyst antibacterial ceramic glaze comprises, by weight, 45 parts of a composite photocatalyst, 35 parts of transparent frit powder, 5 parts of water-washed soil, 0.15 part of sodium hydroxymethyl cellulose and 0.2 part of sodium tripolyphosphate. Wherein: the composite photocatalyst comprises titanium dioxide and tin dioxide, and the titanium dioxide is coated with the tin dioxide; the particle size of the tin dioxide was 25nm.
The preparation method of the photocatalyst antibacterial ceramic glaze comprises the following steps:
(1) 100g of tin dioxide is placed in absolute ethyl alcohol to be stirred, and a dispersion solution is dispersed;
(2) Adding 5mol/L nitric acid into the dispersion solution prepared in the step (1), regulating the pH value of the dispersion solution to 4, dropwise adding 200g of butyl titanate into the dispersion solution, stirring at the speed of 1000r/min for 5 hours at the temperature of 80 ℃, centrifugally washing for 6 times, and drying to obtain a composite photocatalyst;
(3) Mixing the composite photocatalyst prepared in the step (2) with transparent frit powder, water-washed soil, sodium hydroxymethyl cellulose and sodium tripolyphosphate, and adding water for ball milling to prepare the photocatalyst antibacterial ceramic glaze of the embodiment.
A lightweight ceramic tile comprises a green body layer, a ground coat layer and a surface coat layer.
Wherein: the chemical composition of the raw materials of the green body layer comprises the following components in percentage by weight: siO (SiO) 2 59.8％、Al 2 O 3 18％、Fe 2 O 3 0.2％、CaO8％、MgO3％、K 2 O 3％、Na 2 O1% and 7% loss by burning.
The raw materials of the ground coat layer comprise the following raw materials in parts by weight: 7 parts of potassium feldspar, 16 parts of calcite, 23 parts of barium carbonate, 5 parts of zirconium silicate, 8 parts of aluminum oxide, 5 parts of zinc oxide, 20 parts of calcined talcum, 5 parts of calcined kaolin, 6 parts of kaolin and 5 parts of quartz; the viscosity of the primer layer was 850 Pa.s.
The surface glaze layer adopts the photocatalyst antibacterial ceramic glaze material prepared by the embodiment.
The preparation method of the light ceramic tile comprises the following steps:
(1) Grinding the raw materials of the green body layer, performing spray drying granulation, and performing compression molding to obtain the green body layer;
(2) Grinding the ground glaze layer of the embodiment to obtain ground glaze slip;
(3) And (3) sequentially spraying the base glaze slip prepared in the step (2) and the photocatalyst antibacterial ceramic glaze prepared in the embodiment on the surface of the green body layer prepared in the step (1), and preparing the lightweight ceramic tile in the embodiment under the condition that the sintering temperature is 1220 ℃ and the sintering period is 80 minutes.
Comparative example 1
The photocatalyst antibacterial ceramic glaze comprises, by weight, 20 parts of nano titanium dioxide, 25 parts of transparent frit powder, 3.5 parts of water-washed soil, 0.1 part of sodium hydroxymethyl cellulose and 0.15 part of sodium tripolyphosphate.
The preparation method of the photocatalyst antibacterial ceramic glaze comprises the following steps:
the nano titanium dioxide is mixed with transparent frit powder, water-washed soil, sodium hydroxymethyl cellulose and sodium tripolyphosphate, and water is added for ball milling, so that the photocatalyst antibacterial ceramic glaze of the comparative example is prepared.
Comparative example 1 is different from the photocatalyst antibacterial ceramic frit of example 1 in that the comparative example 1 adopts nano titanium dioxide as a photocatalyst, and the composite photocatalyst of example 1 is not added, and the composition and the addition amount of other raw materials are the same as those of example 1.
The lightweight ceramic tile of comparative example 1 was identical in structure, composition and method of preparation to example 1.
Comparative example 2
The photocatalyst antibacterial ceramic glaze comprises, by weight, 20 parts of zinc oxide, 25 parts of transparent frit powder, 3.5 parts of water-washed soil, 0.1 part of sodium hydroxymethyl cellulose, 0.15 part of sodium tripolyphosphate and 20nm of zinc oxide.
The preparation method of the photocatalyst antibacterial ceramic glaze comprises the following steps:
the photocatalyst antibacterial ceramic glaze of the comparative example is prepared by mixing nano zinc oxide with transparent frit powder, water-washed soil, sodium hydroxymethyl cellulose and sodium tripolyphosphate, and adding water for ball milling.
Comparative example 2 is different from the photocatalyst antibacterial ceramic glaze of example 1 in that comparative example 2 adopts nano zinc oxide as a photocatalyst, and the composite photocatalyst of example 1 is not added, and the composition and the addition amount of other raw materials are the same as those of example 1.
The lightweight ceramic tile of comparative example 2 was identical in structure, composition and method of preparation to example 1.
Comparative example 3
The photocatalyst antibacterial ceramic glaze comprises, by weight, 10 parts of zinc oxide, 10 parts of nano titanium dioxide, 25 parts of transparent frit powder, 3.5 parts of water-washed soil, 0.1 part of sodium hydroxymethyl cellulose, 0.15 part of sodium tripolyphosphate and 20nm of zinc oxide.
The preparation method of the photocatalyst antibacterial ceramic glaze comprises the following steps:
the photocatalyst antibacterial ceramic glaze of the comparative example is prepared by mixing nano titanium dioxide and zinc oxide with transparent frit powder, water-washed soil, sodium hydroxymethyl cellulose and sodium tripolyphosphate, and adding water for ball milling.
Comparative example 3 is different from the photocatalyst antibacterial ceramic glaze of example 1 in that comparative example 3 adopts nano titanium dioxide and zinc oxide as a composite photocatalyst formed by direct mixing, and does not adopt nano titanium dioxide to wrap zinc oxide, and the composition and the addition amount of other raw materials are the same as those of example 1.
The lightweight ceramic tile of comparative example 3 was identical in structure, composition and method of preparation to example 1.
Comparative example 4
The composition and preparation method of the photocatalyst antibacterial ceramic glaze of comparative example 4 are the same as those of example 1.
The lightweight ceramic tile of comparative example 4 differs from example 1 in that the base coat layer of comparative example 4 differs from example 1 in the raw material composition, and the green body layer and the cover coat layer are each identical to example 1 in composition. Wherein: the raw materials of the primer layer of comparative example 4 comprise the following raw materials in parts by weight: 14 parts of potassium feldspar, 16 parts of calcite, 20 parts of barium carbonate, 5 parts of zirconium silicate, 8 parts of aluminum oxide, 5 parts of zinc oxide, 20 parts of calcined talcum, 5 parts of calcined kaolin, 8 parts of kaolin and 5 parts of quartz; the viscosity of the primer layer was 300 Pa.s.
The lightweight ceramic tile of comparative example 4 was prepared in the same manner as in example 1.
Performance testing
According to JC/T897-2014 antibacterial ceramic product antibacterial property standard, the light ceramic tile samples obtained in each example and comparative example are subjected to detection of antibacterial rate under different wave band illumination conditions.
The glazed transparency of the light ceramic tile samples obtained in each example and comparative example was tested according to GB/T2680-94 standards for building glass visible light transmittance, solar direct transmittance, solar total transmittance, ultraviolet transmittance and determination of related glass parameters.
The glazed quality of the light ceramic tile samples was also observed and the test results are shown in table 1 below.
Table 1: product performance test comparative table for each example and comparative example
From the results of the product performance tests of the examples and comparative examples in Table 1, it can be seen that: the samples corresponding to examples 1, 2 and 3 have better antibacterial property on escherichia coli and staphylococcus aureus under the irradiation of each wave band, and the samples have good glaze transparency and good decoration. In the comparative example 1, nano titanium dioxide is directly used as a photocatalyst, and the photocatalyst has a good antibacterial effect only when ultraviolet light is irradiated, and the antibacterial property is poor when visible light is irradiated; in comparative example 2, zinc oxide is directly used as a photocatalyst, and the loss is generated at high temperature, so that a better antibacterial effect cannot be exerted under the irradiation of visible light or ultraviolet light, and zinc oxide crystals are not protected by a coating layer and react with other components in the glaze, so that the crystals are separated out, and the transparency of the glaze is reduced; the two photocatalysts of the comparative example 3 do not adopt a wrapped structure, but are directly added into the glaze, so that the antibacterial effect is also not ideal; the lower viscosity of the base glaze of comparative example 4 causes bubbles in the light ceramic tile blank to overflow from the surface glaze layer through the base glaze layer, thereby causing more pinholes on the sintered glaze surface to influence the quality of the glaze surface.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While obvious variations or modifications are contemplated as falling within the scope of the present invention.
Claims (7)
1. The photocatalyst antibacterial ceramic glaze is characterized by comprising a composite photocatalyst, wherein the composite photocatalyst comprises a first photocatalyst and a second photocatalyst, and the first photocatalyst wraps the second photocatalyst;
the first photocatalyst is titanium dioxide; the second photocatalyst is at least one of zinc oxide, silicon nitride and tin dioxide;
the particle size of the second photocatalyst is 5-30nm;
the photocatalyst antibacterial ceramic glaze comprises the following components in parts by weight: 20-45 parts of composite photocatalyst, 25-35 parts of transparent frit powder, 3.5-5 parts of water-washed soil, 0.1-0.15 part of sodium hydroxymethyl cellulose and 0.15-0.2 part of sodium tripolyphosphate.
2. The method for preparing the photocatalyst antibacterial ceramic glaze as claimed in claim 1, which is characterized by comprising the following steps:
(1) Dispersing the second photocatalyst in absolute ethanol to obtain a dispersion solution;
(2) Under the acidic condition, butyl titanate is dropwise added into the dispersion solution, heating and stirring are carried out, and the composite photocatalyst is obtained after washing and drying;
(3) And mixing and grinding the composite photocatalyst, transparent frit powder, water-washed soil, sodium hydroxymethyl cellulose and sodium tripolyphosphate to obtain the photocatalyst antibacterial ceramic glaze.
3. The method for preparing the photocatalyst antibacterial ceramic glaze according to claim 2, wherein the mass ratio of the second photocatalyst to the butyl titanate is 1: (0.5-2).
4. The method for preparing a photocatalyst antibacterial ceramic glaze according to claim 2, wherein in the step (2), the heating temperature is 50-80 ℃, and the stirring speed is 1000-1500r/min.
5. A lightweight ceramic tile comprising a green body layer, a primer layer, and a cover glaze layer, wherein the cover glaze layer is formed by firing the photocatalyst antimicrobial ceramic glaze of claim 1.
6. The lightweight ceramic tile of claim 5, wherein the green layer comprises the following raw materials in weight percent: siO (SiO) 2 55-60％、Al 2 O 3 15-20％、Fe 2 O 3 0.1-0.5％、CaO6-12％、MgO 1-5％、K 2 O 1-5％、Na 2 0.5-1% of O and 5-10% of burning loss; the glaze viscosity of the ground coat layer is 500-1000 Pa.s.
7. The use of the photocatalyst antibacterial ceramic glaze as claimed in claim 1 in the ceramic field.
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