CN114656241A - 一种保健防臭瓷砖及其制备方法 - Google Patents
一种保健防臭瓷砖及其制备方法 Download PDFInfo
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- CN114656241A CN114656241A CN202210387202.0A CN202210387202A CN114656241A CN 114656241 A CN114656241 A CN 114656241A CN 202210387202 A CN202210387202 A CN 202210387202A CN 114656241 A CN114656241 A CN 114656241A
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- Prior art keywords
- ceramic tile
- solution
- mass
- health
- modified resin
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- 239000000919 ceramic Substances 0.000 title claims abstract description 126
- 239000002781 deodorant agent Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 81
- 229920005989 resin Polymers 0.000 claims abstract description 57
- 239000011347 resin Substances 0.000 claims abstract description 57
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000009987 spinning Methods 0.000 claims abstract description 48
- 239000000412 dendrimer Substances 0.000 claims abstract description 39
- 239000013078 crystal Substances 0.000 claims abstract description 28
- 239000003822 epoxy resin Substances 0.000 claims abstract description 28
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 28
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000004332 deodorization Methods 0.000 claims abstract description 25
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 25
- 239000004793 Polystyrene Substances 0.000 claims abstract description 23
- 239000004005 microsphere Substances 0.000 claims abstract description 23
- 229920002223 polystyrene Polymers 0.000 claims abstract description 23
- 238000001354 calcination Methods 0.000 claims abstract description 22
- -1 perfluoroalkyl ethyl bromide Chemical compound 0.000 claims abstract description 20
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- 239000011787 zinc oxide Substances 0.000 claims abstract description 13
- XDXHOMYOYYIQHJ-UHFFFAOYSA-N methyl 5-chloro-2,4-dioxo-1h-pyrimidine-6-carboxylate Chemical compound COC(=O)C=1NC(=O)NC(=O)C=1Cl XDXHOMYOYYIQHJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 210000003298 dental enamel Anatomy 0.000 claims abstract description 5
- 238000004549 pulsed laser deposition Methods 0.000 claims abstract description 3
- 239000010410 layer Substances 0.000 claims description 68
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 60
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 54
- 238000002156 mixing Methods 0.000 claims description 46
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 42
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 42
- 239000008367 deionised water Substances 0.000 claims description 41
- 229910021641 deionized water Inorganic materials 0.000 claims description 41
- 229920000736 dendritic polymer Polymers 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 33
- 239000000835 fiber Substances 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 27
- 239000011159 matrix material Substances 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 26
- 239000011248 coating agent Substances 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- 235000010265 sodium sulphite Nutrition 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- 239000012071 phase Substances 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 17
- 235000019441 ethanol Nutrition 0.000 claims description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 14
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 14
- 239000005457 ice water Substances 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- 239000011701 zinc Substances 0.000 claims description 14
- 229910052725 zinc Inorganic materials 0.000 claims description 14
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000000151 deposition Methods 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 claims description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 7
- 230000036541 health Effects 0.000 claims description 7
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 7
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 7
- 239000008096 xylene Substances 0.000 claims description 7
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000005855 radiation Effects 0.000 claims description 6
- 239000008384 inner phase Substances 0.000 claims description 5
- 239000008385 outer phase Substances 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 239000006004 Quartz sand Substances 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 235000013312 flour Nutrition 0.000 claims description 2
- 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 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000011032 tourmaline Substances 0.000 claims description 2
- 229940070527 tourmaline Drugs 0.000 claims description 2
- 229910052613 tourmaline Inorganic materials 0.000 claims description 2
- 229910052573 porcelain Inorganic materials 0.000 claims 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims 1
- 241000894006 Bacteria Species 0.000 abstract description 8
- 230000003373 anti-fouling effect Effects 0.000 abstract description 6
- 230000002209 hydrophobic effect Effects 0.000 abstract description 6
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 3
- 230000004060 metabolic process Effects 0.000 abstract 1
- 239000002120 nanofilm Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 25
- 239000002002 slurry Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 239000005751 Copper oxide Substances 0.000 description 4
- 229910000431 copper oxide Inorganic materials 0.000 description 4
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 2
- WSMYVTOQOOLQHP-UHFFFAOYSA-N Malondialdehyde Chemical compound O=CCC=O WSMYVTOQOOLQHP-UHFFFAOYSA-N 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 230000037358 bacterial metabolism Effects 0.000 description 2
- 230000001877 deodorizing effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 230000036542 oxidative stress Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
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- 230000003213 activating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
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- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229940118019 malondialdehyde Drugs 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/28—Vacuum evaporation by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/04—Clay; Kaolin
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/16—Lean materials, e.g. grog, quartz
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/32—Burning methods
- C04B33/34—Burning methods combined with glazing
-
- 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
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
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Abstract
本发明公开了一种保健防臭瓷砖及其制备方法,涉及瓷砖技术领域。本发明先对瓷砖坯体进行预处理,增强表面粘着性;接着,以硝酸银为外相溶液、以聚苯乙烯微球为内相溶液纺丝,经高温煅烧下,形成多孔中空结构纳米膜;然后利用脉冲激光沉积形成纳米氧化锌籽晶层,再于锌‑铜源混合溶液中继续生长,形成防臭层,生成电子传递链,可产生活性氧,使细菌窒息而阻止细菌新陈代谢,然后依次包覆釉质层、改性树脂层,其中,改性树脂层由6,7‑二羟基‑4‑杂庚基胺、环氧树脂、2,6‑二羟基‑5‑氯‑4‑嘧啶甲酸甲酯和全氟烷基乙基溴制得,形成疏水性树枝状化合物。本发明制备的保健防臭瓷砖具有防臭、抗污效果。
Description
技术领域
本发明涉及瓷砖技术领域,具体为一种保健防臭瓷砖及其制备方法。
背景技术
随着科学技术的进步和社会的发展,人们越来越关注生活质量等问题,因此保健瓷砖出现人们的视野中,传统带有保健功能的瓷砖,诸如能够施放负离子等功效的瓷砖,实际在使用过程中,并没有达到宣传中的效果,这是因为上述瓷砖中所述的功能性添加物一般都是加入到砖坯中,而瓷砖的表面必须做封釉处理,很难发挥功效,因此本发明将远红外辐射料与面浆混合,将其添加于釉质层中。
此外,保健瓷砖由于防水性能较弱,并且常年暴露在空气中,表面受水体冲刷、粉尘或者其他悬浮颗粒的污染黏附导致墙体受潮、生霉,内部积水严重,易滋生大量细菌,从而产生臭味,极大的破坏了建筑物的美观和使用观感,每年都需花费大量的人力物力清洗、修缮。
发明内容
本发明的目的在于提供一种保健防臭瓷砖及其制备方法,以解决现有技术中存在的问题。
为了解决上述技术问题,本发明提供如下技术方案:一种保健防臭瓷砖,从上至下依次为改性树脂涂层、釉质层、防臭层、瓷砖坯体;所述瓷砖坯体按重量份数计,包括粘土50~70份、高岭土30~40份、镁电气石10~20份、石英15~30份、氧化镁1~5份、羧甲基纤维素1~3份。
进一步的,所述防臭层由以下方法制得,先对陶瓷坯体进行等离子体脉冲轰击预处理,然后以硝酸银溶液为外相溶液、以聚苯乙烯微球溶液为内相溶液,纺丝、高温煅烧得纤维膜瓷砖坯体;再利用脉冲激光沉积得纳米氧化锌籽晶层,然后置于锌-铜源混合溶液中获得防臭层。
进一步的,所述釉质层由面浆烧结制得;所述面浆按重量份数计,包括硅石矿30~40份、轻质碳酸钙6~15份、白泥50~60份、石英砂30~50份、氧化镁1~5份、羧甲基纤维素1~3份、远红外辐射料30~40份、蒸馏水50~60份。
进一步的,所述远红外辐射料为氧化铝、二氧化钛、氧化镁、二氧化锆或二氧化硅的一种或多种混合。
进一步的,所述改性树脂涂层由6,7-二羟基-4-杂庚基胺、环氧树脂、2,6-二羟基-5-氯-4-嘧啶甲酸甲酯和全氟烷基乙基溴制得。
进一步的,一种保健防臭瓷砖的制备方法,包括以下制备步骤:
(1)将瓷砖坯体置于等离子体枪下,抽真空至1×10-3~5×10-3Pa,脉冲3~7次,得预处理瓷砖坯体;以硝酸银纺丝液为外相溶液,以聚苯乙烯微球纺丝液为内相溶液,距离预处理瓷砖坯体15~20cm纺丝至膜层厚度为20~40μm,然后以2~5℃/min升温至500~550℃,煅烧2~5h,得纤维膜瓷砖坯体;
(2)将纤维膜瓷砖坯体置于分子激光器中,抽真空至1×10-4~5×10-4Pa,加热至300~350℃,采用高纯锌靶,纤维膜瓷砖坯体与高纯锌靶间距为5~10cm,以30~70sccm通入氧气至压力为2~6Pa后,沉积5~11min后,得籽晶层瓷砖坯体;将籽晶层瓷砖坯体浸泡于籽晶层瓷砖坯体质量4~12倍的锌-铜源混合溶液中,70~90℃下静置2~5h后,捞出,用去离子水洗涤5~10次,于70~80℃干燥30~42min后,200~250℃煅烧3~6h得防臭层;
(3)向防臭层浇筑面浆至厚度为1~4mm,80~100℃下干燥10~20min后,1100~1300℃下煅烧4~9h,得瓷砖基体;
(4)将E-51环氧树脂、乙二醇单丁醚和无水乙醇按质量比1:0.1:0.1~1:0.4:0.3混合,氮气保护下,升温至65~75℃,搅拌至溶解后,加入E-51环氧树脂质量0.5~0.9倍的6,7-二羟基-4-杂庚基胺,反应8~14h后,加入E-51环氧树脂质量1~4倍的乙醇水溶液,乙醇水溶液中乙醇和水的质量比为0.25:1,静置18~34min得改性树脂基体;
(5)将改性树脂基体、2,6-二羟基-5-氯-4-嘧啶甲酸甲酯、碳酸钾和N,N-二甲基甲酰胺按质量比1:1.1:0.5:35~1:2.4:1.0:43混合,氩气氛围下,加热至70~82℃,100~200rpm下搅拌8~14h后,升温至150~160℃,保温1~3h,然后加改性树脂基体质量60~80倍的二氯甲烷,依次用去离子水、饱和氯化钠溶液洗涤6~13min,38~52℃干燥2~4h,重复上述步骤2~5次得树状化合物;
(6)在冰水浴下,将树状化合物和二氯甲烷按质量比1:18~1:26混合,加入树状化合物质量0.7~1.5倍的全氟烷基乙基溴,100~200rpm下搅拌20~40min后,加入树状化合物质量0.07~0.10倍的N,N-二甲基甲酰胺,撤去冰水浴,于室温反应10~15h,加入树状化合物质量3~5倍的亚硫酸钠溶液、树状化合物质量4~7倍的去离子水,亚硫酸钠溶液中亚硫酸钠和去离子水的质量比为1:9,分液,萃取,依次用去离子水、饱和氯化钠洗涤5~10次,300~400rpm、40~50℃旋蒸2~4h得改性树脂;
(7)按质量比1:0.08:0.02:0.6:0.6~1:0.2:0.05:0.9:0.9将改性树脂、氨乙基哌嗪、聚二甲基硅氧烷、正丁醇和二甲苯混合,得改性树脂涂料;向瓷砖基体喷涂瓷砖基体质量0.1~0.3倍的改性树脂涂料,80~100℃下干燥60~80min,得保健防臭瓷砖。
进一步的,步骤(1)所述硝酸银纺丝液:聚乙烯吡咯烷酮、硝酸银、去离子水和N,N-二甲基甲酰胺按质量比l:1:13:20~1:5:25:33混合,于40~50℃、50~100rpm搅拌2~5h得硝酸银纺丝液;所述聚苯乙烯微球纺丝液:粒径为400~600nm的聚苯乙烯微球和蒸馏水按质量比1:5~1:9混合。
进一步的,步骤(1)所述等离子体枪:脉冲宽度为50~70μs,等离子体的电子密度为1014~1016cm-3,功率密度为105~107W/cm2,离子速度为50~70kms-1;所述纺丝:纺丝电压为15~20kV,内相直径为0.5mm、流速为0.1mL/h,外相直径为1.2mm、流速为0.1~0.3mL/h。
进一步的,步骤(2)所述分子激光器:波长为248nm,脉冲宽度为20~40ns,脉冲重复频率为5~10Hz,脉冲能量为300~400mJ。
进一步的,步骤(2)所述锌-铜源混合溶液:将硝酸锌、六次甲基四胺、硝酸铜和乙二醇按质量比1:0.5:0.3:80~1:0.8:0.5:95混合,加入碳酸钠至溶液pH为7~10。
与现有技术相比,本发明所达到的有益效果是:
本发明在瓷砖坯体上形成多孔防臭层,面浆流入防臭层的通孔和流道,烧结后与瓷砖坯体结合成一体,将防臭层牢牢固定于二者之间,且面浆含有远红外辐射材料,形成具有保健效果的釉质层,再喷涂改性树脂涂层,以实现防臭、抗污的功能。
首先,本发明先对瓷砖坯体进行等离子体脉冲轰击预处理,形成交错沟槽结构,产生分子间交联以强化表面层,增强表面粘着性,有利于防臭层沉积;接着,以硝酸银和聚乙烯吡咯烷酮为外相溶液,以聚苯乙烯微球为内相溶液,纺丝制得纤维膜,经高温煅烧下,硝酸银与聚乙烯吡咯烷酮的羰基发生配位反应,生成纳米银,同时除去聚苯乙烯微球,形成多孔中空结构;然后利用脉冲激光沉积形成纳米氧化锌籽晶层,再于锌-铜源混合溶液中继续生长,形成垂直于纤维膜表面的氧化锌纳米棒,并且表面形成纳米氧化铜颗粒,从而获得防臭层,其自身结构中能够发生电荷的转移,从而生成电子传递链,在接触细菌细胞时,产生羟自由基、超氧阴离子自由基、丙二醛等活性氧,激活氧化应激状态,可催化吸附细菌,使细菌窒息而阻止细菌新陈代谢,且纳米银纤维膜可储存更多的电荷,众多氧化锌、氧化铜纳米结构修饰纳米银纤维膜,使电荷转移效率提高,可增强银与氧化锌、氧化铜之间的电荷转移;此外,防臭层表面能较低,能够起到疏水的效果,减少瓷砖内部积水,防止内部细菌滋生,达到防臭效果。
其次,6,7-二羟基-4-杂庚基胺与环氧树脂的环氧基反应,将其接枝于分子链中,再将2,6-二羟基-5-氯-4-嘧啶甲酸甲酯的氯离子取代6,7-二羟基-4-杂庚基胺的羟基,以此反复,形成树状分子,并用全氟烷基乙基溴封端,从而对环氧树脂进行疏水改性,很好地利用水滴带走粉尘等污染物,使瓷砖具有抗污能力;此外,6,7-二羟基-4-杂庚基胺、2,6-二羟基-5-氯-4-嘧啶甲酸甲酯和全氟烷基乙基溴在环氧树脂表面自发的聚拢,有助于降低表面能,提高涂层稳定性和疏水,提高瓷砖的防污效果,且在胶黏剂的作用下,有效吸附于瓷砖表面,提高瓷砖的抗污使用寿命。
具体实施方式
下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
为了更清楚的说明本发明提供的方法通过以下实施例进行详细说明,在以下实施例中制作的保健防臭瓷砖的各指标测试方法如下:
防臭性:取质量大小相同的实施例与对比例进行抗菌效果测试。
防污性:取质量大小相同的实施例与对比例进行疏水效果测试。
实施例1
一种保健防臭瓷砖的制备方法,所述保健防臭瓷砖的制备方法主要包括以下制备步骤:
(1)将瓷砖坯体置于等离子体枪下,抽真空至1×10-3Pa,脉冲3次,得预处理瓷砖坯体;聚乙烯吡咯烷酮、硝酸银、去离子水和N,N-二甲基甲酰胺按质量比l:1:13:20混合,于40℃、50rpm搅拌5h得硝酸银纺丝液;将粒径为400nm的聚苯乙烯微球和蒸馏水按质量比1:5混合,得聚苯乙烯微球纺丝液;以硝酸银纺丝液为外相溶液,以聚苯乙烯微球纺丝液为内相溶液,距离预处理瓷砖坯体15cm纺丝至膜层厚度为20μm,然后以2℃/min升温至500℃,煅烧5h,得纤维膜瓷砖坯体;所述等离子体枪:脉冲宽度为50μs,等离子体的电子密度为1014cm-3,功率密度为105W/cm2,离子速度为50kms-1;所述纺丝:纺丝电压为15kV,内相直径为0.5mm、流速为0.1mL/h,外相直径为1.2mm、流速为0.1mL/h;
(2)将纤维膜瓷砖坯体置于分子激光器中,抽真空至1×10-4Pa,加热至300℃,采用高纯锌靶,纤维膜瓷砖坯体与高纯锌靶间距为5cm,以30sccm通入氧气至压力为2Pa后,沉积11min后,得籽晶层瓷砖坯体;将硝酸锌、六次甲基四胺、硝酸铜和乙二醇按质量比1:0.5:0.3:80混合,加入碳酸钠至溶液pH为7,得锌-铜源混合溶液;将籽晶层瓷砖坯体浸泡于籽晶层瓷砖坯体质量4倍的锌-铜源混合溶液中,70℃下静置5h后,捞出,用去离子水洗涤5次,于70℃干燥42min后,200℃煅烧6h得防臭层;所述分子激光器:波长为248nm,脉冲宽度为20ns,脉冲重复频率为5Hz,脉冲能量为300mJ;
(3)向防臭层浇筑面浆至厚度为1mm,80℃下干燥20min后,1100℃下煅烧9h,得瓷砖基体;
(4)将E-51环氧树脂、乙二醇单丁醚和无水乙醇按质量比1:0.1:0.1混合,氮气保护下,升温至65℃,搅拌至溶解后,加入E-51环氧树脂质量0.5倍的6,7-二羟基-4-杂庚基胺,反应14h后,加入E-51环氧树脂质量1倍的乙醇水溶液,乙醇水溶液中乙醇和水的质量比为0.25:1,静置18min得改性树脂基体;
(5)将改性树脂基体、2,6-二羟基-5-氯-4-嘧啶甲酸甲酯、碳酸钾和N,N-二甲基甲酰胺按质量比1:1.1:0.5:35混合,氩气氛围下,加热至70℃,100rpm下搅拌14h后,升温至150℃,保温3h,然后加改性树脂基体质量60倍的二氯甲烷,依次用去离子水、饱和氯化钠溶液洗涤6min,38℃干燥4h,重复上述步骤2次得树状化合物;
(6)在冰水浴下,将树状化合物和二氯甲烷按质量比1:18混合,加入树状化合物质量0.7倍的全氟烷基乙基溴,100rpm下搅拌40min后,加入树状化合物质量0.07倍的N,N-二甲基甲酰胺,撤去冰水浴,于室温反应10h,加入树状化合物质量3倍的亚硫酸钠溶液、树状化合物质量4倍的去离子水,亚硫酸钠溶液中亚硫酸钠和去离子水的质量比为1:9,分液,萃取,依次用去离子水、饱和氯化钠洗涤5次,300rpm、40℃旋蒸4h得改性树脂;
(7)按质量比1:0.08:0.02:0.6:0.6将改性树脂、氨乙基哌嗪、聚二甲基硅氧烷、正丁醇和二甲苯混合,得改性树脂涂料;向瓷砖基体喷涂瓷砖基体质量0.1倍的改性树脂涂料,80℃干燥80min,得保健防臭瓷砖。
实施例2
一种保健防臭瓷砖的制备方法,所述保健防臭瓷砖的制备方法主要包括以下制备步骤:
(1)将瓷砖坯体置于等离子体枪下,抽真空至3×10-3Pa,脉冲5次,得预处理瓷砖坯体;聚乙烯吡咯烷酮、硝酸银、去离子水和N,N-二甲基甲酰胺按质量比l:3:19:26.5混合,于45℃搅拌3.5h得硝酸银纺丝液;将粒径为500nm的聚苯乙烯微球和蒸馏水按质量比1:7混合,得聚苯乙烯微球纺丝液;以硝酸银纺丝液为外相溶液,以聚苯乙烯微球纺丝液为内相溶液,距离预处理瓷砖坯体18cm纺丝至膜层厚度为30μm,然后以3℃/min升温至525℃,煅烧3.5h,得纤维膜瓷砖坯体;所述等离子体枪:脉冲宽度为60μs,等离子体的电子密度为1015cm-3,功率密度为106W/cm2,离子速度为60kms-1;所述纺丝:纺丝电压为18kV,内相直径为0.5mm、流速为0.1mL/h,外相直径为1.2mm、流速为0.2mL/h;
(2)将纤维膜瓷砖坯体置于分子激光器中,抽真空至3×10-4Pa,加热至325℃,采用高纯锌靶,纤维膜瓷砖坯体与高纯锌靶间距为8cm,以50sccm通入氧气至压力为4Pa后,沉积8min后,得籽晶层瓷砖坯体;将硝酸锌、六次甲基四胺、硝酸铜和乙二醇按质量比1:0.65:0.4:87.5混合,加入碳酸钠至溶液pH为8.5,得锌-铜源混合溶液;将籽晶层瓷砖坯体浸泡于籽晶层瓷砖坯体质量8倍的锌-铜源混合溶液中,80℃下静置3.5h后,捞出,用去离子水洗涤7次,于75℃干燥36min后,225℃煅烧4.5h得防臭层;所述分子激光器:波长为248nm,脉冲宽度为30ns,脉冲重复频率为7Hz,脉冲能量为350mJ;
(3)向防臭层浇筑面浆至厚度为2.5mm,90℃下干燥15min后,1200℃下煅烧6.5h,得瓷砖基体;
(4)将E-51环氧树脂、乙二醇单丁醚和无水乙醇按质量比1:0.25:0.2混合,氮气保护下,升温至70℃,搅拌至溶解后,加入E-51环氧树脂质量0.7倍的6,7-二羟基-4-杂庚基胺,反应11h后,加入E-51环氧树脂质量1~4倍的乙醇水溶液,乙醇水溶液中乙醇和水的质量比为0.25:1,静置26min得改性树脂基体;
(5)将改性树脂基体、2,6-二羟基-5-氯-4-嘧啶甲酸甲酯、碳酸钾和N,N-二甲基甲酰胺按质量比1:1.75:0.75:39混合,氩气氛围下,加热至76℃,150rpm下搅拌11h后,升温至155℃,保温2h,然后加改性树脂基体质量70倍的二氯甲烷,依次用去离子水、饱和氯化钠溶液洗涤10min,40℃干燥3h,重复上述步骤3次得树状化合物;
(6)在冰水浴下,将树状化合物和二氯甲烷按质量比1:22混合,加入树状化合物质量1.1倍的全氟烷基乙基溴,150rpm下搅拌30min后,加入树状化合物质量0.08倍的N,N-二甲基甲酰胺,撤去冰水浴,于室温反应12.5h,加入树状化合物质量4倍的亚硫酸钠溶液、树状化合物质量5.5倍的去离子水,亚硫酸钠溶液中亚硫酸钠和去离子水的质量比为1:9,分液,萃取,依次用去离子水、饱和氯化钠洗涤7次,350rpm、45℃旋蒸3h得改性树脂;
(7)按质量比1:0.14:0.035:0.75:0.75将改性树脂、氨乙基哌嗪、聚二甲基硅氧烷、正丁醇和二甲苯混合,得改性树脂涂料;向瓷砖基体喷涂瓷砖基体质量0.2倍的改性树脂涂料,90℃干燥70min,得保健防臭瓷砖。
实施例3
一种保健防臭瓷砖的制备方法,所述保健防臭瓷砖的制备方法主要包括以下制备步骤:
(1)将瓷砖坯体置于等离子体枪下,抽真空至5×10-3Pa,脉冲7次,得预处理瓷砖坯体;聚乙烯吡咯烷酮、硝酸银、去离子水和N,N-二甲基甲酰胺按质量比1:5:25:33混合,于50℃搅拌2h得硝酸银纺丝液;将粒径为600nm的聚苯乙烯微球和蒸馏水按质量比1:9混合,得聚苯乙烯微球纺丝液;以硝酸银纺丝液为外相溶液,以聚苯乙烯微球纺丝液为内相溶液,距离预处理瓷砖坯体20cm纺丝至膜层厚度为40μm,然后以5℃/min升温至550℃,煅烧2h,得纤维膜瓷砖坯体;所述等离子体枪:脉冲宽度为70μs,等离子体的电子密度为1016cm-3,功率密度为107W/cm2,离子速度为70kms-1;所述纺丝:纺丝电压为20kV,内相直径为0.5mm、流速为0.1mL/h,外相直径为1.2mm、流速为0.3mL/h;
(2)将纤维膜瓷砖坯体置于分子激光器中,抽真空至5×10-4Pa,加热至350℃,采用高纯锌靶,纤维膜瓷砖坯体与高纯锌靶间距为10cm,以70sccm通入氧气至压力为6Pa后,沉积5min后,得籽晶层瓷砖坯体;将硝酸锌、六次甲基四胺、硝酸铜和乙二醇按质量比1:0.8:0.5:95混合,加入碳酸钠至溶液pH为10,得锌-铜源混合溶液;将籽晶层瓷砖坯体浸泡于籽晶层瓷砖坯体质量12倍的锌-铜源混合溶液中,90℃下静置2h后,捞出,用去离子水洗涤10次,于80℃干燥30min后,250℃煅烧3h得防臭层;所述分子激光器:波长为248nm,脉冲宽度为40ns,脉冲重复频率为10Hz,脉冲能量为400mJ;
(3)向防臭层浇筑面浆至厚度为4mm,100℃下干燥10min后,1300℃下煅烧4h,得瓷砖基体;
(4)将E-51环氧树脂、乙二醇单丁醚和无水乙醇按质量比1:0.4:0.3混合,氮气保护下,升温至75℃,搅拌至溶解后,加入E-51环氧树脂质量0.9倍的6,7-二羟基-4-杂庚基胺,反应14h后,加入E-51环氧树脂质量4倍的乙醇水溶液,乙醇水溶液中乙醇和水的质量比为0.25:1,静置34min得改性树脂基体;
(5)将改性树脂基体、2,6-二羟基-5-氯-4-嘧啶甲酸甲酯、碳酸钾和N,N-二甲基甲酰胺按质量比1:2.4:1.0:43混合,氩气氛围下,加热至82℃,200rpm下搅拌8h后,升温至160℃,保温1h,然后加改性树脂基体质量80倍的二氯甲烷,依次用去离子水、饱和氯化钠溶液洗涤13min,52℃干燥2h,重复上述步骤5次得树状化合物;
(6)在冰水浴下,将树状化合物和二氯甲烷按质量比1:26混合,加入树状化合物质量1.5倍的全氟烷基乙基溴,200rpm下搅拌20min后,加入树状化合物质量0.10倍的N,N-二甲基甲酰胺,撤去冰水浴,于室温反应15h,加入树状化合物质量5倍的亚硫酸钠溶液、树状化合物质量7倍的去离子水,亚硫酸钠溶液中亚硫酸钠和去离子水的质量比为1:9,分液,萃取,依次用去离子水、饱和氯化钠洗涤10次,400rpm、50℃旋蒸2h得改性树脂;
(7)按质量比1:0.2:0.05:0.9:0.9将改性树脂、氨乙基哌嗪、聚二甲基硅氧烷、正丁醇和二甲苯混合,得改性树脂涂料;向瓷砖基体喷涂瓷砖基体质量0.3倍的改性树脂涂料,100℃干燥60min,得保健防臭瓷砖。
对比例1
对比例1与实施例2的区别仅在于步骤(1)的不同,将步骤(1)改为:将聚乙烯吡咯烷酮、硝酸银、去离子水和N,N-二甲基甲酰胺按质量比l:3:19:26.5混合,于45℃搅拌3.5h得硝酸银纺丝液;将粒径为500nm的聚苯乙烯微球和蒸馏水按质量比1:7混合,得聚苯乙烯微球纺丝液;以硝酸银纺丝液为外相溶液,以聚苯乙烯微球纺丝液为内相溶液,距离瓷砖坯体18cm纺丝至膜层厚度为30μm,然后以3℃/min升温至525℃,煅烧3.5h,得纤维膜瓷砖坯体;所述等离子体枪:脉冲宽度为60μs,等离子体的电子密度为1015cm-3,功率密度为106W/cm2,离子速度为60kms-1;所述纺丝:纺丝电压为18kV,内相直径为0.5mm、流速为0.1mL/h,外相直径为1.2mm、流速为0.2mL/h。其余步骤同实施例2。
对比例2
一种保健防臭瓷砖的制备方法,所述保健防臭瓷砖的制备方法主要包括以下制备步骤:
(1)将瓷砖坯体置于等离子体枪下,抽真空至3×10-3Pa,脉冲5次,得预处理瓷砖坯体;将预处理瓷砖坯体置于分子激光器中,抽真空至3×10-4Pa,加热至325℃,采用高纯锌靶,纤维膜瓷砖坯体与高纯锌靶间距为8cm,以50sccm通入氧气至压力为4Pa后,沉积8min后,得籽晶层瓷砖坯体;将硝酸锌、六次甲基四胺、硝酸铜和乙二醇按质量比1:0.65:0.4:87.5混合,加入碳酸钠至溶液pH为8.5,得锌-铜源混合溶液;将籽晶层瓷砖坯体浸泡于籽晶层瓷砖坯体质量8倍的锌-铜源混合溶液中,80℃下静置3.5h后,捞出,用去离子水洗涤7次,于75℃干燥36min后,225℃煅烧4.5h得防臭层;所述分子激光器:波长为248nm,脉冲宽度为30ns,脉冲重复频率为7Hz,脉冲能量为350mJ;
(2)向防臭层浇筑面浆至厚度为2.5mm,90℃下干燥15min后,1200℃下煅烧6.5h,得瓷砖基体;
(3)将E-51环氧树脂、乙二醇单丁醚和无水乙醇按质量比1:0.25:0.2混合,氮气保护下,升温至70℃,搅拌至溶解后,加入E-51环氧树脂质量0.7倍的6,7-二羟基-4-杂庚基胺,反应11h后,加入E-51环氧树脂质量1~4倍的乙醇水溶液,乙醇水溶液中乙醇和水的质量比为0.25:1,静置26min得改性树脂基体;
(4)将改性树脂基体、2,6-二羟基-5-氯-4-嘧啶甲酸甲酯、碳酸钾和N,N-二甲基甲酰胺按质量比1:1.75:0.75:39混合,氩气氛围下,加热至76℃,150rpm下搅拌11h后,升温至155℃,保温2h,然后加改性树脂基体质量70倍的二氯甲烷,依次用去离子水、饱和氯化钠溶液洗涤10min,40℃干燥3h,重复上述步骤3次得树状化合物;
(5)在冰水浴下,将树状化合物和二氯甲烷按质量比1:22混合,加入树状化合物质量1.1倍的全氟烷基乙基溴,150rpm下搅拌30min后,加入树状化合物质量0.08倍的N,N-二甲基甲酰胺,撤去冰水浴,于室温反应12.5h,加入树状化合物质量4倍的亚硫酸钠溶液、树状化合物质量5.5倍的去离子水,亚硫酸钠溶液中亚硫酸钠和去离子水的质量比为1:9,分液,萃取,依次用去离子水、饱和氯化钠洗涤7次,350rpm、45℃旋蒸3h得改性树脂;
(6)按质量比1:0.14:0.035:0.75:0.75将改性树脂、氨乙基哌嗪、聚二甲基硅氧烷、正丁醇和二甲苯混合,得改性树脂涂料;向瓷砖基体喷涂瓷砖基体质量0.2倍的改性树脂涂料,90℃干燥70min,得保健防臭瓷砖。
对比例3
对比例3与实施例2的区别仅在于步骤(2)的不同,将步骤(2)改为:将硝酸锌、六次甲基四胺、硝酸铜和乙二醇按质量比1:0.65:0.4:87.5混合,加入碳酸钠至溶液pH为8.5,得锌-铜源混合溶液;将纤维膜瓷砖坯体浸泡于籽晶层瓷砖坯体质量8倍的锌-铜源混合溶液中,80℃下静置3.5h后,捞出,用去离子水洗涤7次,于75℃干燥36min后,225℃煅烧4.5h得防臭层;所述分子激光器:波长为248nm,脉冲宽度为30ns,脉冲重复频率为7Hz,脉冲能量为350mJ。其余制备步骤同实施例2。
对比例4
对比例4与实施例2的区别仅在于步骤(2)的不同,将步骤(2)改为:将纤维膜瓷砖坯体置于分子激光器中,抽真空至3×10-4Pa,加热至325℃,采用高纯锌靶,纤维膜瓷砖坯体与高纯锌靶间距为8cm,以50sccm通入氧气至压力为4Pa后,沉积8min后,得防臭层;所述分子激光器:波长为248nm,脉冲宽度为30ns,脉冲重复频率为7Hz,脉冲能量为350mJ。其余制备步骤同实施例2。
对比例5
对比例5与实施例2的区别在于无步骤(4),步骤(5)改为:将E-51环氧树脂、2,6-二羟基-5-氯-4-嘧啶甲酸甲酯、碳酸钾和N,N-二甲基甲酰胺按质量比1:1.75:0.75:39混合,氩气氛围下,加热至76℃,150rpm下搅拌11h后,升温至155℃,保温2h,然后加E-51环氧树脂质量70倍的二氯甲烷,依次用去离子水、饱和氯化钠溶液洗涤10min,40℃干燥3h,重复上述步骤3次得树状化合物。其余制备步骤同实施例2。
对比例6
对比例6与实施例2的区别在于无步骤(5),步骤(6)改为:在冰水浴下,将改性树脂基体和二氯甲烷按质量比1:22混合,加入改性树脂基体质量1.1倍的全氟烷基乙基溴,150rpm下搅拌30min后,加入改性树脂基体质量0.08倍的N,N-二甲基甲酰胺,撤去冰水浴,于室温反应12.5h,加入改性树脂基体质量4倍的亚硫酸钠溶液、改性树脂基体质量5.5倍的去离子水,亚硫酸钠溶液中亚硫酸钠和去离子水的质量比为1:9,分液,萃取,依次用去离子水、饱和氯化钠洗涤7次,350rpm、45℃旋蒸3h得改性树脂。其余步骤同实施例2。
对比例7
对比例7与实施例2的区别在于无步骤(6),步骤(7)改为:按质量比1:0.14:0.035:0.75:0.75将树状化合物、氨乙基哌嗪、聚二甲基硅氧烷、正丁醇和二甲苯混合,得改性树脂涂料;向瓷砖基体喷涂瓷砖基体质量0.2倍的改性树脂涂料,90℃干燥70min,得保健防臭瓷砖。其余步骤同实施例2。
效果例
下表1给出了采用本发明实施例1至3与对比例1至7的保健防臭瓷砖的性能分析结果。
表1
抗菌率(%) | 水接触角(°) | |
实施例1 | 99.7 | 155.2 |
实施例2 | 99.9 | 156.1 |
实施例3 | 99.6 | 155.8 |
对比例1 | 70.3 | 154.3 |
对比例2 | 71.3 | 154.7 |
对比例3 | 72.6 | 154.6 |
对比例4 | 72.8 | 154.7 |
对比例5 | 96.8 | 90.2 |
对比例6 | 96.8 | 96.3 |
对比例7 | 97.0 | 99.1 |
从实施例与对比例的抗菌率实验数据对比可发现,本发明先对陶瓷坯体进行等离子体脉冲轰击预处理,有利于防臭层沉积;接着,依次制备多孔中空纳米银纤维膜、纳米氧化锌籽晶层、氧化锌纳米棒和纳米氧化铜颗粒,生成电子传递链,在接触细菌细胞时,产生羟自由基、超氧阴离子自由基、丙二醛等活性氧,激活氧化应激状态,可催化吸附细菌,使细菌窒息而阻止细菌新陈代谢;从实施例与对比例的疏水角实验数据比较可发现,6,7-二羟基-4-杂庚基胺、2,6-二羟基-5-氯-4-嘧啶甲酸甲酯和全氟烷基乙基溴改性环氧树脂,对其进行疏水改性,很好地利用水滴带走粉尘等污染物,使瓷砖具有抗污能力;此外,6,7-二羟基-4-杂庚基胺、2,6-二羟基-5-氯-4-嘧啶甲酸甲酯和全氟烷基乙基溴在环氧树脂表面自发的聚拢,有助于降低表面能,提高涂层稳定性和疏水。
对于本领域技术人员而言,显然本发明不限于上述示范性实施例的细节,而且在不背离本发明的精神或基本特征的情况下,能够以其他的具体形式实现本发明。因此,无论从哪一点来看,均应将实施例看作是示范性的,而且是非限制性的,本发明的范围由所附权利要求而不是上述说明限定,因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明内。不应将权利要求中的任何标记视为限制所涉及的权利要求。
Claims (10)
1.一种保健防臭瓷砖,其特征在于,从上至下依次为改性树脂涂层、釉质层、防臭层、瓷砖坯体;所述瓷砖坯体按质量分数计,包括粘土50~70份、高岭土30~40份、镁电气石10~20份、石英15~30份、氧化镁1~5份、羧甲基纤维素1~3份。
2.根据权利要求1所述的一种保健防臭瓷砖,其特征在于,所述防臭层由以下方法制得,先对陶瓷坯体进行等离子体脉冲轰击预处理,然后以硝酸银溶液为外相溶液、以聚苯乙烯微球溶液为内相溶液,纺丝、高温煅烧得纤维膜瓷砖坯体;再利用脉冲激光沉积得纳米氧化锌籽晶层,然后置于锌-铜源混合溶液中获得防臭层。
3.根据权利要求1所述的一种保健防臭瓷砖,其特征在于,所述釉质层由面浆烧结制得;所述面浆按重量份数计,包括硅石矿30~40份、轻质碳酸钙6~15份、白泥50~60份、石英砂30~50份、氧化镁1~5份、羧甲基纤维素1~3份、远红外辐射料30~40份、蒸馏水50~60份。
4.根据权利要求3所述的一种保健防臭瓷砖,其特征在于,所述远红外辐射料为氧化铝、二氧化钛、氧化镁、二氧化锆或二氧化硅的一种或多种混合。
5.根据权利要求1所述的一种保健防臭瓷砖,其特征在于,所述改性树脂涂层由6,7-二羟基-4-杂庚基胺、环氧树脂、2,6-二羟基-5-氯-4-嘧啶甲酸甲酯和全氟烷基乙基溴制得。
6.一种保健防臭瓷砖的制备方法,其特征在于,包括以下制备步骤:
(1)将瓷砖坯体置于等离子体枪下,抽真空至1×10-3~5×10-3Pa,脉冲3~7次,得预处理瓷砖坯体;以硝酸银纺丝液为外相溶液,以聚苯乙烯微球纺丝液为内相溶液,距离预处理瓷砖坯体15~20cm纺丝至膜层厚度为20~40μm,然后以2~5℃/min升温至500~550℃,煅烧2~5h,得纤维膜瓷砖坯体;
(2)将纤维膜瓷砖坯体置于分子激光器中,抽真空至1×10-4~5×10-4Pa,加热至300~350℃,采用高纯锌靶,纤维膜瓷砖坯体与高纯锌靶间距为5~10cm,以30~70sccm通入氧气至压力为2~6Pa后,沉积5~11min后,得籽晶层瓷砖坯体;将籽晶层瓷砖坯体浸泡于籽晶层瓷砖坯体质量4~12倍的锌-铜源混合溶液中,70~90℃下静置2~5h后,捞出,用去离子水洗涤5~10次,于70~80℃干燥30~42min后,200~250℃煅烧3~6h得防臭层;
(3)向防臭层浇筑面浆至厚度为1~4mm,80~100℃下干燥10~20min后,1100~1300℃下煅烧4~9h,得瓷砖基体;
(4)将E-51环氧树脂、乙二醇单丁醚和无水乙醇按质量比1:0.1:0.1~1:0.4:0.3混合,氮气保护下,升温至65~75℃,搅拌至溶解后,加入E-51环氧树脂质量0.5~0.9倍的6,7-二羟基-4-杂庚基胺,反应8~14h后,加入E-51环氧树脂质量1~4倍的乙醇水溶液,乙醇水溶液中乙醇和水的质量比为0.25:1,静置18~34min得改性树脂基体;
(5)将改性树脂基体、2,6-二羟基-5-氯-4-嘧啶甲酸甲酯、碳酸钾和N,N-二甲基甲酰胺按质量比1:1.1:0.5:35~1:2.4:1.0:43混合,氩气氛围下,加热至70~82℃,100~200rpm下搅拌8~14h后,升温至150~160℃,保温1~3h,然后加改性树脂基体质量60~80倍的二氯甲烷,依次用去离子水、饱和氯化钠溶液洗涤6~13min,38~52℃干燥2~4h,重复上述步骤2~5次得树状化合物;
(6)在冰水浴下,将树状化合物和二氯甲烷按质量比1:18~1:26混合,加入树状化合物质量0.7~1.5倍的全氟烷基乙基溴,100~200rpm下搅拌20~40min后,加入树状化合物质量0.07~0.10倍的N,N-二甲基甲酰胺,撤去冰水浴,于室温反应10~15h,加入树状化合物质量3~5倍的亚硫酸钠溶液、树状化合物质量4~7倍的去离子水,亚硫酸钠溶液中亚硫酸钠和去离子水的质量比为1:9,分液,萃取,依次用去离子水、饱和氯化钠洗涤5~10次,300~400rpm、40~50℃旋蒸2~4h得改性树脂;
(7)按质量比1:0.08:0.02:0.6:0.6~1:0.2:0.05:0.9:0.9将改性树脂、氨乙基哌嗪、聚二甲基硅氧烷、正丁醇和二甲苯混合,得改性树脂涂料;向瓷砖基体喷涂瓷砖基体质量0.1~0.3倍的改性树脂涂料,80~100℃干燥60~80min,得保健防臭瓷砖。
7.根据权利要求6所述的一种保健防臭瓷砖的制备方法,其特征在于,步骤(1)所述硝酸银纺丝液:聚乙烯吡咯烷酮、硝酸银、去离子水和N,N-二甲基甲酰胺按质量比l:1:13:20~1:5:25:33混合,于40~50℃、50~100rpm搅拌2~5h得硝酸银纺丝液;所述聚苯乙烯微球纺丝液:粒径为400~600nm的聚苯乙烯微球和蒸馏水按质量比1:5~1:9混合。
8.根据权利要求6所述的一种保健防臭瓷的制备方法,其特征在于,步骤(1)所述等离子体枪:脉冲宽度为50~70μs,等离子体的电子密度为1014~1016cm-3,功率密度为105~107W/cm2,离子速度为50~70kms-1;所述纺丝:纺丝电压为15~20kV,内相直径为0.5mm、流速为0.1mL/h,外相直径为1.2mm、流速为0.1~0.3mL/h。
9.根据权利要求6所述的一种保健防臭瓷的制备方法,其特征在于,步骤(2)所述分子激光器:波长为248nm,脉冲宽度为20~40ns,脉冲重复频率为5~10Hz,脉冲能量为300~400mJ。
10.根据权利要求6所述的一种保健防臭瓷的制备方法,其特征在于,步骤(2)所述锌-铜源混合溶液:将硝酸锌、六次甲基四胺、硝酸铜和乙二醇按质量比1:0.5:0.3:80~1:0.8:0.5:95混合,加入碳酸钠至溶液pH为7~10。
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