CN111233325A - Nano TiO (titanium dioxide)2Self-cleaning functional ceramic and preparation method and application thereof - Google Patents
Nano TiO (titanium dioxide)2Self-cleaning functional ceramic and preparation method and application thereof Download PDFInfo
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- CN111233325A CN111233325A CN202010122521.XA CN202010122521A CN111233325A CN 111233325 A CN111233325 A CN 111233325A CN 202010122521 A CN202010122521 A CN 202010122521A CN 111233325 A CN111233325 A CN 111233325A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 143
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 238000004140 cleaning Methods 0.000 title claims abstract description 69
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 67
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 43
- 239000011159 matrix material Substances 0.000 claims description 30
- 239000002245 particle Substances 0.000 claims description 26
- 239000000377 silicon dioxide Substances 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 18
- 238000010304 firing Methods 0.000 claims description 16
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 238000005507 spraying Methods 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 3
- 230000006870 function Effects 0.000 abstract description 16
- 230000001954 sterilising effect Effects 0.000 abstract description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 8
- 241000894006 Bacteria Species 0.000 abstract description 7
- 238000005286 illumination Methods 0.000 abstract description 6
- 239000001569 carbon dioxide Substances 0.000 abstract description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 4
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 abstract description 4
- 238000013032 photocatalytic reaction Methods 0.000 abstract description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 3
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 2
- 230000000593 degrading effect Effects 0.000 abstract description 2
- 230000001877 deodorizing effect Effects 0.000 abstract description 2
- 239000011941 photocatalyst Substances 0.000 abstract description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 239000000292 calcium oxide Substances 0.000 description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 10
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 238000004659 sterilization and disinfection Methods 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 6
- 229910052682 stishovite Inorganic materials 0.000 description 6
- 229910052905 tridymite Inorganic materials 0.000 description 6
- 230000003115 biocidal effect Effects 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910001948 sodium oxide Inorganic materials 0.000 description 5
- 238000004887 air purification Methods 0.000 description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 4
- 238000004332 deodorization Methods 0.000 description 4
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005034 decoration Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910001950 potassium oxide Inorganic materials 0.000 description 3
- 238000004017 vitrification Methods 0.000 description 3
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/14—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silica
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/86—Glazes; Cold glazes
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
- E04F13/00—Coverings or linings, e.g. for walls or ceilings
- E04F13/07—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor
- E04F13/08—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements
- E04F13/14—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements stone or stone-like materials, e.g. ceramics concrete; of glass or with an outer layer of stone or stone-like materials or glass
- E04F13/142—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements stone or stone-like materials, e.g. ceramics concrete; of glass or with an outer layer of stone or stone-like materials or glass with an outer layer of ceramics or clays
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
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- C04B2235/02—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
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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Abstract
The invention relates to the technical field of ceramic materials, and provides nano TiO2Self-cleaning functional ceramic and a preparation method and application thereof. The invention provides nano TiO2The glaze layer of the self-cleaning functional ceramic contains 3-7 parts by mass of titanium dioxide, after the titanium dioxide in the glaze layer is illuminated, the contact angle between the surface of the ceramic and water drops or oil drops can be greatly reduced, the surface of the ceramic is completely soaked by water or oil, so that stains on the surface of the ceramic can be easily washed by water, and the surface of the ceramic is kept clean; under the condition of solar illumination, the titanium dioxide in the glaze layer can absorb light with the wavelength of 280-320 nm in light waves to generate a photocatalytic reaction, and organic matters such as formaldehyde, bacteria and the like can be decomposed into carbon dioxide and water. The invention provides nano TiO2The self-cleaning functional ceramic has the functions of self-cleaning, degrading organic matters by the photocatalyst, resisting bacteria, sterilizing, preventing fouling, deodorizing and purifying air.
Description
Technical Field
The invention relates to the technical field of ceramic materials, in particular to nano TiO2Self-cleaning functional ceramic and a preparation method and application thereof.
Background
The ceramic product has wide application in building decoration materials, such as decorative wall tiles and the like. The contact angle of the surface of the ceramic product and the liquid directly determines the self-cleaning degree of the surface of the ceramic product. For an ideal solid surface, the contact angle is the most intuitive method for judging whether the liquid can wet the surface, and when theta is less than 90 degrees, the liquid can be wetted; theta >90 deg. is not wetted. Researches show that the larger the contact angle is, the less spread of the liquid drop is, and the more round the water drop shape is; the smaller the contact angle, the easier the droplet spreads, and the closer to the water film, the better the self-cleaning effect.
At present, the contact angle between a common ceramic glaze surface and water is large, so water easily forms water drops on the common ceramic surface, the water drops are not easy to slide off, dust in air is easily adsorbed in the process of drying the water drops, water marks are formed after drying, and dirt is formed for a long time.
Disclosure of Invention
In view of the above, the present invention provides a nano TiO2Self-cleaning functional ceramic, preparation method and application thereof, and nano TiO provided by the invention2The self-cleaning functional ceramic has super-hydrophilic surface, and when contacting with water, water drops are on the nano TiO2The surface of the self-cleaning functional ceramic forms a uniform water film, under the action of the water film, stains on the surface of the ceramic can be easily washed by water, so that the surface of the ceramic is kept clean, the stains on the surface of the outer wall of the ceramic can be washed clean by outdoor natural rainfall, and the self-cleaning function is achieved.
The invention provides a nano TiO2The self-cleaning functional ceramic comprises a ceramic substrate and a glaze layer;the glaze layer comprises the following chemical components in parts by mass:
preferably, the thickness of the glaze layer is 340-360 mu m.
Preferably, the particle size of the titanium dioxide in the glaze layer is 5-20 microns, wherein the volume percentage of the titanium dioxide with the particle size of 5-8 microns is 75-85%.
Preferably, the particle size of the silicon dioxide is less than or equal to 50 μm; the grain diameter of the aluminum oxide is less than or equal to 50 mu m.
Preferably, the chemical composition of the ceramic matrix comprises the following substances in parts by mass:
the invention also provides the nano TiO in the technical scheme2The preparation method of the self-cleaning functional ceramic comprises the following steps:
(1) providing a ceramic matrix;
(2) spraying glaze water on the surface of the ceramic substrate, and then firing to obtain nano TiO2 self-cleaning functional ceramic; the glaze water is prepared from a glaze layer raw material and water.
Preferably, the firing temperature is 1050-1150 ℃, and the firing time is 50 min-6 h.
Preferably, the preparation method of the ceramic matrix comprises the following steps:
mixing raw materials for preparing a ceramic matrix, and then sequentially performing drying, crushing, sieving, granulating and pressing treatment to obtain a dry blank;
sintering the dry blank to obtain a ceramic matrix; the sintering temperature is 1350-1420 ℃, and the sintering time is 60 min-8 h.
The invention also provides the nano TiO in the technical scheme2The self-cleaning functional ceramic is applied to the outer wall of a building.
Advantageous effects
The invention provides a nano TiO2Self-cleaning functional ceramic, nano TiO provided by the invention2The glaze layer of the self-cleaning functional ceramic contains 3-7 parts by mass of titanium dioxide, after the titanium dioxide in the glaze layer is illuminated, the contact angle between the surface of the ceramic and water drops or oil drops can be greatly reduced, the surface of the ceramic is completely soaked by water or oil to form a uniform water film or oil film, namely, the ceramic has super-amphiphilicity (super-hydrophilicity and super-lipophilicity), under the action of the water film or the oil film, stains on the surface of the ceramic can be easily washed by water, so that the surface of the ceramic is kept clean, outdoor natural rainfall can wash the stains on the surface of the ceramic (such as an outer wall) clean, and the self-cleaning function is realized. Under the condition of solar illumination, the titanium dioxide in the glaze layer can absorb light with the wavelength of 280-320 nm in light waves to generate a photocatalytic reaction, so that oxygen and water molecules attached to the surface of the ceramic are excited to generate OH with super activity-And O2The free radicals with strong oxidizing property can decompose organic matters such as formaldehyde, bacteria and the like into carbon dioxide and water, so that the nano TiO provided by the invention2The self-cleaning functional ceramic has the functions of photocatalytic degradation of organic matters, antibiosis, sterilization, pollution prevention, deodorization and air purification. In the invention, the silicon dioxide, the aluminum oxide, the calcium oxide and the sodium oxide in the glaze layer are beneficial to improving the interface bonding acting force of the glaze layer and the ceramic substrate and provide a beneficial environment for better playing the role of the titanium dioxide. Under the combined action of all components of the glaze layer, the nano TiO provided by the invention2The self-cleaning functional ceramic has the functions of self-cleaning, degrading organic matters by the photocatalyst, resisting bacteria, sterilizing, preventing fouling, deodorizing and purifying air.
Detailed Description
The invention provides a nano TiO2Self-cleaning functional ceramic, the nano TiO2The self-cleaning functional ceramic comprises a ceramic substrate and a glaze layer; the glaze layer comprises the following chemical components in parts by mass:
in the present invention, the nano TiO2The glaze layer of the self-cleaning functional ceramic comprises 80-90 parts by mass of silicon dioxide, preferably 82-88 parts by mass, and more preferably 84-87 parts by mass; the particle size of the silicon dioxide is preferably less than or equal to 50 mu m; the silicon dioxide in the glaze layer has vitrification effect on the self-cleaning function of the ceramic, and is beneficial to ensure that the nano TiO2The self-cleaning functional ceramic has a super-hydrophilic surface.
In the invention, the nano TiO is based on the mass part of the silicon dioxide2The glaze layer of the self-cleaning functional ceramic comprises 1-3 parts by mass of aluminum oxide, preferably 1.5 parts, 2.0 parts, 2.5 parts or 3.0 parts; the grain diameter of the aluminum oxide is preferably less than or equal to 50 mu m; the aluminum oxide is added into the glaze layer, so that the ceramic provided by the invention is mild, fine and white as jade in appearance, the water absorption of the ceramic can be reduced, and the ceramic has the characteristics of oxidation resistance, corrosion resistance, no discoloration and long service life.
In the invention, the nano TiO is based on the mass part of the silicon dioxide2The glaze layer of the self-cleaning functional ceramic comprises 1-5 parts by mass of calcium oxide, preferably 1-4 parts, and more preferably 1-3 parts; the calcium oxide in the glaze layer has vitrification effect on the self-cleaning function of the ceramic, and is beneficial to ensure that the nano TiO2The self-cleaning functional ceramic has a super-hydrophilic surface.
In the invention, the nano TiO is based on the mass part of the silicon dioxide2The glaze layer of the self-cleaning functional ceramic comprises 1-3 parts by mass of sodium oxide, preferably 1-2 parts, and more preferably 1-1.5 parts; the sodium oxide in the glaze layer has vitrification effect on the self-cleaning function of the ceramic, and is beneficial to ensure that the nano TiO2The self-cleaning functional ceramic has a super-hydrophilic surface.
In the invention, the nano TiO is based on the mass part of the silicon dioxide2The glaze layer of the self-cleaning functional ceramic comprises 3-7 parts by mass of titanium dioxide, preferably 3-6 parts, more preferably 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts or 5.5 parts. In the invention, the particle size of the titanium dioxide in the glaze layer is preferably 5-20 μm, and more preferably 10-15 μm; wherein the particle size is 5 to EThe volume percentage of the titanium dioxide of 8 μm is preferably 75 to 85%. In the invention, after the titanium dioxide in the glaze layer is illuminated, the contact angle between the ceramic surface and water drops or oil drops is greatly reduced, the ceramic surface is completely soaked by water to form a layer of uniform water film or oil film, namely, the water film or oil film has super-amphiphilicity (super-hydrophilicity and super-lipophilicity), under the action of the water film or oil film, stains on the ceramic surface can be easily washed by water, so that the ceramic surface is kept clean, and the stains on the ceramic surface (such as an outer wall) can be washed clean by outdoor natural rainfall, thereby realizing the self-cleaning function. Under the condition of solar illumination, the titanium dioxide in the glaze layer can absorb light with the wavelength of 280-320 nm in light waves to generate a photocatalytic reaction, so that oxygen and water molecules attached to the surface of the ceramic are excited to generate OH with super activity-And O2The free radicals with strong oxidizing property can decompose organic matters such as formaldehyde, bacteria and the like into carbon dioxide and water, so that the nano TiO provided by the invention2The self-cleaning functional ceramic has the functions of photocatalytic degradation of organic matters, antibiosis, sterilization, pollution prevention, deodorization and air purification. In the present invention, the particle size of titanium dioxide is preferably controlled within the above range, which is advantageous for better exhibiting the effect of titanium dioxide.
In the present invention, the nano TiO2The thickness of the glaze layer in the self-cleaning functional ceramic is preferably 340-360 mu m, and more preferably 350 mu m. The invention preferably controls the thickness of the glaze layer within the range, so that the nano TiO provided by the invention2The self-cleaning functional ceramic has the functions of self-cleaning, antibiosis, sterilization, antifouling, deodorization and air purification.
In the present invention, the chemical composition of the ceramic matrix preferably includes the following substances in parts by mass:
in the present invention, the mass fraction of the substance in the ceramic base is different from the mass fraction of the substance in the glaze layer.
In the present invention, the ceramic base preferably includes 70 to 75 parts by mass of silica, and more preferably 72 to 74 parts. On the basis of the mass parts of silicon dioxide in the ceramic matrix, the ceramic matrix preferably comprises 20-25 parts of aluminum oxide, more preferably 21-24 parts of aluminum oxide, and even more preferably 22-23 parts of aluminum oxide; the ceramic matrix preferably comprises 6.0-6.5 parts by mass of potassium oxide, and more preferably 6.2-6.3 parts by mass of potassium oxide; the ceramic matrix preferably comprises 0.1-0.3 parts by mass of sodium oxide, and more preferably 0.2 part; the ceramic matrix preferably includes 0.5 to 1.0 part by mass of iron oxide, and more preferably 0.7 to 0.8 part by mass. The invention preferably controls the quality of silicon dioxide, aluminum oxide, potassium oxide, sodium oxide and ferric oxide in the ceramic matrix within the range, which is beneficial to ensuring that the ceramic matrix and the glaze layer have better interface acting force and the glaze layer can be more firmly attached to the surface of the ceramic matrix. In the present invention, the ceramic matrix preferably further includes a trace amount of calcium oxide and magnesium oxide.
In the present invention, the method for preparing the ceramic substrate preferably comprises the steps of: mixing raw materials for preparing a ceramic matrix, and then sequentially performing drying, crushing, sieving, granulating and pressing treatment to obtain a dry blank; sintering the dry blank to obtain a ceramic matrix; the sintering temperature is 1350-1420 ℃, and the sintering time is 60 min-8 h. In the present invention, the raw material for preparing the ceramic matrix is preferably clay satisfying the above-mentioned material ratio. In the invention, the water content of the material obtained after drying is preferably less than or equal to 3 percent; the mesh number of the screen for sieving is preferably 150 meshes; the pressing treatment is preferably performed by a 100T two-way dry press. In the invention, the sintering temperature is preferably 1380-1420 ℃, and more preferably 1400 ℃.
The invention also provides the nano TiO in the technical scheme2The preparation method of the self-cleaning functional ceramic comprises the following steps:
(1) providing a ceramic matrix;
(2) spraying glaze water on the surface of the ceramic substrate, and then firing to obtain nano TiO2Self-cleaning functional ceramics; the glaze water is prepared from a glaze layer raw material and water.
The ceramic matrix is prepared according to the method.
After the ceramic matrix is obtained, the invention sprays glaze water on the surface of the ceramic matrix, and then carries out firing to obtain the nano TiO2Self-cleaning functional ceramics. In the present invention, the chemical composition of the glaze water preferably includes the following substances in parts by mass:
in the present invention, the mass parts of the substances in the glaze water and the mass parts of the substances in the ceramic matrix are different from each other.
In the invention, the water in the glaze water is preferably 5 to 35 parts by mass, more preferably 5 to 30 parts by mass, and even more preferably 5 to 25 parts by mass. The glaze water is sprayed on the surface of the ceramic substrate, and the spraying method is well known to those skilled in the art, and the spraying method is not particularly required by the invention.
After the spraying is finished, the ceramic matrix sprayed with the glaze water is fired to obtain the nano TiO2Self-cleaning functional ceramics. In the present invention, the firing temperature is preferably 1050 to 1150 ℃, and the firing time is preferably 50min to 6 hours, more preferably 3 hours to 6 hours, and even more preferably 3 hours, 4 hours, 5 hours, or 6 hours.
The invention also provides the nano TiO in the technical scheme2The self-cleaning functional ceramic is applied to the outer wall of a building.
The invention provides nano TiO2The self-cleaning functional ceramic is used as an external wall of a building, and TiO in the ceramic is exposed to sunlight2After illumination, water drops on the surface of the ceramic can form a super-hydrophilic surface and form a uniform water film, and under the action of the water film, stains on the surface of the ceramic can be easily washed by water, so that the surface of the ceramic is kept clean, and the stains on the surface (outer wall) of the ceramic can be washed clean by outdoor natural rainfall, thereby realizing the self-cleaning function. Under the condition of solar illumination, the titanium dioxide in the glaze layer can absorb light with the wavelength of 280-320 nm in light waves to generate a photocatalytic reaction, so that oxygen and water molecules attached to the surface of the ceramic are excited to generate OH with super activity-And O2The free radicals with strong oxidizing property can decompose organic matters, bacteria and the like attached to the surface of the outer wall into carbon dioxide and water, so that the nano TiO provided by the invention2The self-cleaning functional ceramic has the functions of antibiosis, sterilization, antifouling, deodorization and air purification.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1
(1) Drying 90kg of soil with the water content of 3%, crushing into fine particles, sieving with a 150-mesh sieve, granulating, filling the particles into a die, and pressing by using a 100T bidirectional dry press to obtain a dry blank; the main chemical components and the mass fraction thereof in the dry blank are as follows: al (Al)2O321％、SiO272％、K2O 6.1％、Na2O 0.11％、Fe2O30.7 percent of other trace components of CaO and MgO;
firing the dry blank at 1360 ℃ for 7.5h to obtain a ceramic matrix;
(2) spraying glaze water on the surface of the ceramic substrate, and then firing at 1100 ℃ for 6h to obtain nano TiO2Self-cleaning functional ceramics; the glaze water comprises the main chemical components and the mass ratio of SiO2：Al2O3：CaO：NaO：TiO2：H2O85: 2: 1.5: 1.5: 3: 7, wherein the particle size of the silicon dioxide is less than or equal to 50 μm; the grain diameter of the aluminum oxide is less than or equal to 50 mu m; the titanium dioxide has a particle size of 5-20 μm, and the volume percentage of titanium dioxide having a particle size of 5-8 μm in the titanium dioxide is 75%.
Example 2
Preparing a ceramic substrate according to the method of example 1;
spraying glaze water on the surface of the ceramic substrate, and then firing at 1050 ℃ for 5h to obtain nano TiO2Self-cleaning functional ceramics; the glaze water comprises the main chemical components and the mass ratio of SiO2：Al2O：CaO：NaO：TiO2：H2O84: 3: 1.5: 1.5: 3.5: 6.5, wherein the particle size of the silicon dioxide is less than or equal to 50 mu m; of aluminium oxideThe grain diameter is less than or equal to 50 mu m; the titanium dioxide has a particle size of 5-20 μm, and the volume percentage of titanium dioxide having a particle size of 5-8 μm in the titanium dioxide is 85%.
Example 3
Preparing a ceramic substrate according to the method of example 1;
spraying glaze water on the surface of the ceramic substrate, and then firing at 1150 ℃ for 4h to obtain nano TiO2Self-cleaning functional ceramics; the glaze water comprises the main chemical components and the mass ratio of SiO2：Al2O：CaO：NaO：TiO2：H2O84.5: 2: 1.5: 1.5: 4: 6.5, wherein the particle size of the silicon dioxide is less than or equal to 50 mu m; the grain diameter of the aluminum oxide is less than or equal to 50 mu m; the titanium dioxide has a particle size of 5-20 μm, and the volume percentage of titanium dioxide having a particle size of 5-8 μm in the titanium dioxide is 80%.
Example 4
Preparing a ceramic substrate according to the method of example 1;
spraying glaze water on the surface of the ceramic substrate, and then firing at 1100 ℃ for 6h to obtain nano TiO2Self-cleaning functional ceramics; the glaze water comprises the main chemical components and the mass ratio of SiO2：Al2O：CaO：NaO：TiO2：H2O84.5: 1.5: 1.5: 1.5: 4.5: 6.5, wherein the particle size of the silicon dioxide is less than or equal to 50 mu m; the grain diameter of the aluminum oxide is less than or equal to 50 mu m; the titanium dioxide has a particle size of 5-20 μm, and the volume percentage of titanium dioxide having a particle size of 5-8 μm in the titanium dioxide is 78%.
Example 5
Preparing a ceramic substrate according to the method of example 1;
spraying glaze water on the surface of the ceramic substrate, and then firing at 1100 ℃ for 6h to obtain nano TiO2Self-cleaning functional ceramics; the glaze water comprises the main chemical components and the mass ratio of SiO2：Al2O：CaO：NaO：TiO2：H2O86.5: 1: 1: 1: 4: 6.5, wherein the particle size of the silicon dioxide is less than or equal to 50 mu m; the grain diameter of the aluminum oxide is less than or equal to 50 mu m; the titanium dioxide has a particle size of 5-20 μm, and the volume percentage of titanium dioxide having a particle size of 5-8 μm in the titanium dioxide is 82%.
For the nano TiO prepared in example 12The formaldehyde degradation rate of the self-cleaning functional ceramic is tested, and the test method comprises the following steps:
the nano TiO prepared in example 12The self-cleaning functional ceramics are respectively put into an environmental climate box, the temperature of the environmental climate box is kept at (23 +/-2) ° C, the humidity is kept at (50 +/-5)%, and a light source is a 40W daylight lamp. Injecting a fixed amount of formaldehyde into the environmental climate box, then extracting the gas in the environmental climate box every 1h, and detecting the content of formaldehyde in the environmental climate box. The result shows that the formaldehyde degradation rate can reach 93 percent within 8 hours under visible light.
For the nano TiO prepared in example 12The antibacterial rate of the self-cleaning functional ceramic is tested, and the test method comprises the following steps:
nano TiO prepared in example 120.1mL of bacterial liquid (staphylococcus aureus and escherichia coli) is coated on the surface of the self-cleaning functional ceramic, and viable bacteria are cultured and counted and the sterilization rate is calculated by adopting a pouring method after the visible light illumination is carried out for 24 hours. The result shows that the sterilization rate reaches 99% under visible light.
In conclusion, the nano TiO provided by the invention2The self-cleaning ceramic has self-cleaning function, and has photocatalysis function and sterilization and antibiosis function.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. Nano TiO (titanium dioxide)2The self-cleaning functional ceramic is characterized by comprising a ceramic substrate and a glaze layer; the glaze layer comprises the following chemical components in parts by mass:
2. according to claimThe nano TiO of claim 12The self-cleaning functional ceramic is characterized in that the thickness of the glaze layer is 340-360 mu m.
3. Nano TiO according to claim 1 or 22The self-cleaning functional ceramic is characterized in that the particle size of titanium dioxide in the glaze layer is 5-20 microns, wherein the volume percentage of the titanium dioxide with the particle size of 5-8 microns is 75-85%.
4. Nano-TiO according to claim 12The self-cleaning functional ceramic is characterized in that the particle size of the silicon dioxide is less than or equal to 50 mu m; the grain diameter of the aluminum oxide is less than or equal to 50 mu m.
5. Nano-TiO according to claim 12The self-cleaning functional ceramic is characterized in that the chemical components of the ceramic matrix comprise the following substances in parts by mass:
6. the nano TiO of any one of claims 1 to 52The preparation method of the self-cleaning functional ceramic is characterized by comprising the following steps:
(1) providing a ceramic matrix;
(2) spraying glaze water on the surface of the ceramic substrate, and then firing to obtain nano TiO2Self-cleaning functional ceramics; the glaze water is prepared from a glaze layer raw material and water.
7. The preparation method according to claim 6, wherein the firing temperature is 1050 to 1150 ℃ and the firing time is 50min to 6 h.
8. The method according to claim 6, wherein the ceramic matrix is prepared by a method comprising the steps of:
mixing raw materials for preparing a ceramic matrix, and then sequentially performing drying, crushing, sieving, granulating and pressing treatment to obtain a dry blank;
sintering the dry blank to obtain a ceramic matrix; the sintering temperature is 1350-1420 ℃, and the sintering time is 60 min-8 h.
9. The nano TiO of any one of claims 1 to 52Self-cleaning functional ceramic or nano TiO prepared by the preparation method of any one of claims 6 to 82The self-cleaning functional ceramic is applied to the outer wall of a building.
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