CN106630632B - A kind of preparation method with photo-catalysis function zirconic acid bismuth micro-crystalline ceramic glaze - Google Patents
A kind of preparation method with photo-catalysis function zirconic acid bismuth micro-crystalline ceramic glaze Download PDFInfo
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- CN106630632B CN106630632B CN201611219629.0A CN201611219629A CN106630632B CN 106630632 B CN106630632 B CN 106630632B CN 201611219629 A CN201611219629 A CN 201611219629A CN 106630632 B CN106630632 B CN 106630632B
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 39
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 35
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 24
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000002253 acid Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000011222 crystalline ceramic Substances 0.000 title description 4
- 229910002106 crystalline ceramic Inorganic materials 0.000 title description 4
- 239000000919 ceramic Substances 0.000 claims abstract description 48
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000010304 firing Methods 0.000 claims abstract description 19
- 239000002689 soil Substances 0.000 claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004615 ingredient Substances 0.000 claims abstract description 16
- 239000002270 dispersing agent Substances 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 13
- 229910052656 albite Inorganic materials 0.000 claims abstract description 6
- 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 claims abstract description 6
- 229910021538 borax Inorganic materials 0.000 claims abstract description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 6
- 239000010453 quartz Substances 0.000 claims abstract description 6
- 238000010791 quenching Methods 0.000 claims abstract description 6
- 230000000171 quenching effect Effects 0.000 claims abstract description 6
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 6
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000004321 preservation Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 5
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 5
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical group [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 238000003801 milling Methods 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 8
- 239000011159 matrix material Substances 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- 238000005034 decoration Methods 0.000 abstract description 2
- 210000003298 dental enamel Anatomy 0.000 abstract description 2
- 230000006872 improvement Effects 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 3
- 229940043267 rhodamine b Drugs 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000015895 biscuits Nutrition 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/20—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing titanium compounds; containing zirconium compounds
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
-
- B01J35/39—
-
- 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
- C04B41/50—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
- C04B41/5023—Glass-ceramics
-
- 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
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/86—Glazes; Cold glazes
Abstract
A kind of preparation method with photo-catalysis function zirconic acid bismuth ceramic glaze, by quartz, potassium feldspar, albite, borax, Bi2O3, Suzhou soil, after lithium carbonate ingredient in 1270-1290 DEG C of heat preservation 20-40min, taking-up is poured into water quenching and frit is made；Frit is ground, A material is obtained；By A material and Bi2O3、ZrO2And Suzhou soil ingredient, obtain B material；B material and dispersing agent are added to the water, stirs and evenly mixs and is configured to glaze slip；By glaze slip glazing in ceramic surface, firing is obtained with photo-catalysis function zirconic acid bismuth ceramic glaze.Enamel glossiness produced by the present invention is good, and chemical property is stablized.The present invention prepares ceramic glaze using the technique of firing, it does not need to carry out plated film, so that the function ceramics glaze of preparation is tightly combined with ceramic matrix, it is not easily to fall off, and the crystallization crystalline substance flower of special appearance can be quickly formed in frit surface, surface decoration effect is good.
Description
Technical field
The invention belongs to the technical fields of ceramic glaze.There is photo-catalysis function zirconic acid bismuth micro-crystalline ceramic more particularly to one kind
The preparation method of glaze.
Background technique
Photocatalysis technology starts from 1972, Japanese scholars Fujishima and Honda discovery on semi-conducting electrode can light urge
Change decomposition water and prepares hydrogen [Fujishima A., Honda K.Photocatalysis-decomposition of water
at the surface of an irradiated semiconductor[J].Nature,1972,238(5385):37-
38.], this discovery causes scientific worker and greatly pays close attention to photocatalysis.With the energy and environmental problem to become increasingly conspicuous,
Photocatalysis technology is widely paid attention to and obtains rapid development.Catalysis material has degradable organic pollutant, purification empty
The application potential of gas, antibacterial and automatically cleaning etc..
Since construction sanitary ceramic and domestic ceramics are present in the every aspect of human lives, as modern humans' environmental protection is anticipated
The environmental requirement of ceramic product is also gradually increased in the enhancing of knowledge.Thus, function ceramics enters the visual field of people.Wherein
It just include photocatalysis ceramics.Ceramics with photo-catalysis function can will be adsorbed in ceramics under conditions of available light irradiates
Organic pollutant, bacterium, the toxic gas molecular degradation on surface, to achieve the purpose that automatically cleaning, antibacterial and purification air
[David F Ollis.Photocatalytic purification and remediation ofcontaminated air
and water[J].Chemistry,2000,3:405-411.]。
Photocatalysis ceramics preparation process is generally divided into 2 classes: first is that photochemical catalyst is added in ceramic glaze, then by usually pottery
Porcelain technique is sintered to obtain self-cleaning ceramic；Second is that thin in the photochemical catalyst that conventional ceramic surface is coated with one layer of tens nm or several hundred nm
[Liu Ping, Dai Wenxin wait On Photocatalytic Functional Ceramics and its light degradation characteristic [J] environmental science, 2004,25 (4): 109- to film
112.].The shortcomings that above method, or there are photocatalysis film and matrix associativity are poor, loss easy to fall off, or there are photocatalysis
Be unevenly distributed in agent glaze, exist " rainbow effect " the disadvantages of, directly affect ceramics aesthetics.
Summary of the invention
It is an object of the invention to propose a kind of preparation method with photo-catalysis function zirconic acid bismuth micro-crystalline ceramic glaze, the glaze
Expect simultaneously synthesizing photochemical catalyst during the preparation process, it is uniformly beautiful, it is good with ceramic matrix adhesive force, while photocatalytic degradation is organic
Pollutant is had excellent performance, and in traditional ceramics field, the surfaces such as such as building hygiene and domestic ceramics are had a wide range of applications.
To achieve the above object, the present invention adopts the following technical scheme that:
A kind of preparation method with photo-catalysis function zirconic acid bismuth ceramic glaze, includes the following steps:
1) firstly, by quartz, potassium feldspar, albite, borax, Bi2O3, Suzhou soil, lithium carbonate is according to mass ratio SiO2:
Al2O3: B2O3: Bi2O3: Li2O:Na2O:K2O=(57-59): (4-6): (22-24): (2-4): (5-7): (2-4): (1-3) into
Row ingredient；
2) powder after ingredient is dry-mixed and grind, sieving obtains mixture, and mixture is kept the temperature at 1270-1290 DEG C
20-40min, taking-up are poured into water quenching and frit are made；Frit is ground, A material is obtained；
3) by A material and Bi2O3、ZrO2And Suzhou soil is A material: Bi according to mass ratio2O3: ZrO2: Suzhou soil=(82-
86): (7-7.4): (2.6-3): the proportion of (5-7) carries out ingredient, and grinding obtains B material；Wherein, Bi2O3With ZrO2Substance amount
Ratio meet Bi4Zr3O12In stoichiometric ratio；
4) B material and dispersing agent are added to the water, stir and evenly mix and is configured to glaze slip；
5) glaze slip glazing is burnt into after dry through roller kilns oxidizing flame, firing temperature 1110-1160 in ceramic surface
DEG C, firing period total time is 40-50 minutes, and soaking time is 6-8 minutes under firing temperature, is obtained with photo-catalysis function zirconium
Sour bismuth ceramic glaze.
A further improvement of the present invention lies in that grinding is carried out in ball grinder in step 2) and step 3, and frit:
Ball: water quality ratio is 1:1:0.8, and milling time is 3-5 hours.
A further improvement of the present invention lies in that the mass content of water is 44-50% in glaze slip in step 4).
A further improvement of the present invention lies in that the mass content of dispersing agent is 0.05-0.15% in glaze slip.
A further improvement of the present invention lies in that dispersing agent is sodium carboxymethylcellulose in step 4).
A further improvement of the present invention lies in that carrying out glazing using glaze spraying mode in step 5).
A further improvement of the present invention lies in that glazing is in step 5) with a thickness of 0.2-0.4mm.
A further improvement of the present invention lies in that temperature dry in step 5) is 60-80 DEG C.
A further improvement of the present invention lies in that firing atmosphere is oxidizing atmosphere in step 5).
Compared with prior art, the invention has the benefit that
1. the present invention obtains the ceramic glaze with photo-catalysis function using firing process, wherein zirconic acid bismuth crystallite component can
To have good intermiscibility with the silicate in biscuit of ceramics, so enamel glossiness obtained is good, chemical property is stablized.
2. the present invention prepares ceramic glaze using the technique of firing, do not need to carry out plated film, so that the function pottery of preparation
Glaze is tightly combined with ceramic matrix, not easily to fall off, Bi2O3、ZrO2The photochemical catalyst zirconic acid bismuth generated during the sintering process exists
Be evenly distributed in glaze, not generating " rainbow effect " influences glaze aesthetics, and can quickly be formed in frit surface it is special
The crystallization crystalline substance flower of pattern, surface decoration effect are good.
3. raw material uses Suzhou soil, contain a small amount of TiO in ingredient2, be conducive to the photocatalysis performance for promoting glaze.This hair
The glaze of bright preparation has photo-catalysis function, and Ceramic glaze can have organic pollutant after 8 hours under illumination condition
There is catalyticing decomposition action, photocatalysis effect test, test result table are carried out to glaze layer using BL-GHX-V type photochemical reactor
The bright resolution ratio to dyestuffs such as rhodamine B and methylene blues can achieve 92%.
4. glaze prepared by the present invention has the spy in visible light wave range high absorptivity and the high-transmission rate to infrared light
Point, photocatalytic ingredient have good visible light-responded.
Detailed description of the invention
Fig. 1 is the Bi that 1 glaze layer surface of embodiment is precipitated4Zr3O12Crystallite SEM figure.
Fig. 2 is 1 glaze layer photocatalytic degradation rhodamine B efficiency chart of embodiment.
Specific embodiment
The present invention is described in detail with reference to the accompanying drawing.
In the present invention in Suzhou soil based on mass percentage, contain 37%~39% Al2O3, 46%~48%
SiO2。
Embodiment 1
1) firstly, by quartz, potassium feldspar, albite, borax, Bi2O3, Suzhou soil, the raw materials such as lithium carbonate are according to following quality
Chemical constituent proportion carries out ingredient.SiO2: Al2O3: B2O3: Bi2O3: Li2O:Na2O:K2O=57:4:22:4:7:4:3.
2) above-mentioned powder is dry-mixed and grind, it crosses 60 meshes and obtains mixture, be fitted into crucible, be put into electric furnace 1270
DEG C heat preservation 20min, taking-up be poured into water quenching be made frit.Frit is taken out from water, be put into after drying it is levigate in ball grinder,
Control material (frit): ball: water quality ratio is 1:1:0.8, crosses 250 meshes after grinding 3 hours, is dried for standby.The powder is denoted as A
Material.
3) above-mentioned A is expected and Bi2O3、ZrO2And Suzhou soil is A:Bi according to mass ratio2O3: Suzhou soil=82:7.4:7
Proportion carries out ingredient, and Bi2O3With ZrO2The ratio of amount of substance meet Bi4Zr3O12In stoichiometric ratio, be uniformly mixed simultaneously
Levigate in ball grinder, control material: ball: water quality ratio is 1:1:0.8, crosses 250 meshes after grinding 3 hours, is dried for standby.The powder
Material is denoted as B material.
4) B material and dispersing agent are added to the water, stir and evenly mix and be configured to glaze slip, the mass content of water is in glaze slip
44%, the mass content of dispersing agent is 0.05%, and dispersing agent is sodium carboxymethylcellulose.
5) use the glazing of glaze spraying mode in ceramic surface above-mentioned prepared glaze slip, glazing is with a thickness of 0.4mm, at 60 DEG C
Under the conditions of it is dry after be burnt into through roller kilns oxidizing flame, firing temperature is 1110 DEG C, and firing period is 40 minutes, is protected under firing temperature
The warm time is 6 minutes, is obtained with photo-catalysis function zirconic acid bismuth ceramic glaze.
Fig. 1 is the SEM figure that crystallite is precipitated in the glaze layer surface prepared under the conditions of embodiment 1, as can be seen from the figure
Bi4Zr3O12The microscopic appearance of photocatalytic ingredient is Nanoparticulate.Between 30-65nm, average grain diameter is about crystallite dimension
50nm。
Fig. 2 is rhdamine B of degrading under the glaze layer surface simulation visible light conditions prepared under the conditions of embodiment 1,
Middle to use 1000W xenon lamp simulated visible light, the rhodamine B that degradation concentration is 3mg/L, after irradiation in 8 hours, degradation efficiency reaches
92%.
Embodiment 2
1) firstly, by quartz, potassium feldspar, albite, borax, Bi2O3, Suzhou soil, the raw materials such as lithium carbonate are according to following quality
Chemical constituent proportion carries out ingredient.SiO2: Al2O3: B2O3: Bi2O3: Li2O:Na2O:K2O=58:5:23:3:6:3:2.
2) above-mentioned powder is dry-mixed and grind, it crosses 60 meshes and obtains mixture, be fitted into crucible, be put into electric furnace 1280
DEG C heat preservation 30min, taking-up be poured into water quenching be made frit.Frit is taken out from water, be put into after drying it is levigate in ball grinder,
Control material (frit): ball: water quality ratio is 1:1:0.8, crosses 250 meshes after grinding 4 hours, is dried for standby.The powder is denoted as A
Material.
3) above-mentioned A is expected and Bi2O3、ZrO2And Suzhou soil is A:Bi according to mass ratio2O3: Suzhou soil=84:7.2:6
Proportion carries out ingredient, and Bi2O3With ZrO2The ratio of amount of substance meet Bi4Zr3O12In stoichiometric ratio, be uniformly mixed simultaneously
Levigate in ball grinder, control material: ball: water quality ratio is 1:1:0.8, crosses 250 meshes after grinding 4 hours, is dried for standby.The powder
Material is denoted as B material.
4) B is expected that addition water stirs and evenly mixs and is configured to glaze slip, the mass content for controlling water is 47%, while quality is added and contains
Amount is 0.10% sodium carboxymethylcellulose as dispersing agent.
5) use the glazing of glaze spraying mode in ceramic surface above-mentioned prepared glaze slip, glazing is with a thickness of 0.3mm, at 70 DEG C
Under the conditions of it is dry after be burnt into through roller kilns oxidizing flame, firing temperature is 1135 DEG C, and firing period is 45 minutes, is protected under firing temperature
The warm time is 7 minutes, is obtained with photo-catalysis function zirconic acid bismuth ceramic glaze.
Embodiment 3
1) firstly, by quartz, potassium feldspar, albite, borax, Bi2O3, Suzhou soil, the raw materials such as lithium carbonate are according to following quality
Chemical constituent proportion carries out ingredient.SiO2: Al2O3: B2O3: Bi2O3: Li2O:Na2O:K2O=59:6:24:2:5:2:1.
2) above-mentioned powder is dry-mixed and grind, it crosses 40 meshes and obtains mixture, be fitted into crucible, be put into electric furnace 1290
DEG C heat preservation 40min, taking-up be poured into water quenching be made frit.Frit is taken out from water, be put into after drying it is levigate in ball grinder,
Control material (frit): ball: water quality ratio is 1:1:0.8, crosses 250 meshes after grinding 3 hours, is dried for standby.The powder is denoted as A
Material.
3) above-mentioned A is expected and Bi2O3、ZrO2And Suzhou soil is A:Bi according to mass ratio2O3: Suzhou soil=86:7:5 matches
Than carrying out ingredient, and Bi2O3With ZrO2The ratio of amount of substance meet Bi4Zr3O12In stoichiometric ratio, be uniformly mixed and in
Levigate in ball grinder, control material: ball: water quality ratio is 1:1:0.8, crosses 250 meshes after grinding 5 hours, is dried for standby.The powder
It is denoted as B material.
4) B material and dispersing agent are added to the water, stir and evenly mix and be configured to glaze slip, the mass content of water is in glaze slip
50%, the mass content of dispersing agent is 0.15% in glaze slip, and dispersing agent is sodium carboxymethylcellulose.
5) use the glazing of glaze spraying mode in ceramic surface above-mentioned prepared glaze slip, glazing is with a thickness of 0.2mm, at 80 DEG C
Under the conditions of it is dry after be burnt into through roller kilns oxidizing flame, firing temperature is 1160 DEG C, and firing period is 50 minutes, is protected under firing temperature
The warm time is 8 minutes, is obtained with photo-catalysis function zirconic acid bismuth ceramic glaze.
The present invention may be implemented directly to synthesize the crystallite with photo-catalysis function simultaneously during prepared by glaze, can
Effectively overcome the problems, such as that above method exists.In addition, because bismuth series photocatalyst has good photocatalysis effect synthesis
Zirconic acid bismuth play good incrustation effect except can quickly form the crystallization crystalline substance flower with special appearance in frit surface
Fruit, it is important that there is good visible light catalytic effect.Different from TiO2With poor visible light-responded, zirconic acid bismuth exists
Under natural light irradiation, also there is good photocatalysis effect to the pollutant for being adsorbed on frit surface.Therefore, from environmentally protective
Angle sees that the innovation for architectural pottery and domestic ceramics has huge meaning.
Claims (8)
1. a kind of preparation method with photo-catalysis function zirconic acid bismuth ceramic glaze, which comprises the steps of:
1) firstly, by quartz, potassium feldspar, albite, borax, Bi2O3, Suzhou soil, lithium carbonate is according to mass ratio SiO2: Al2O3:
B2O3: Bi2O3: Li2O:Na2O:K2O=(57-59): (4-6): (22-24): (2-4): (5-7): (2-4): (1-3) is matched
Material；
2) powder after ingredient is dry-mixed and grind, sieving obtains mixture, by mixture in 1270-1290 DEG C of heat preservation 20-
40min, taking-up are poured into water quenching and frit are made；Frit is ground, A material is obtained；
3) by A material and Bi2O3、ZrO2And Suzhou soil is A material: Bi according to mass ratio2O3: ZrO2: Suzhou soil=(82-86): (7-
7.4): (2.6-3): the proportion of (5-7) carries out ingredient, and grinding obtains B material；Wherein, Bi2O3With ZrO2Substance amount ratio it is full
Sufficient Bi4Zr3O12In stoichiometric ratio；
4) B material and dispersing agent are added to the water, stir and evenly mix and is configured to glaze slip；
5) glaze slip glazing is burnt into after dry through roller kilns oxidizing flame in ceramic surface, firing temperature is 1110-1160 DEG C, is burnt
It is 40-50 minutes at total time in period, soaking time is 6-8 minutes under firing temperature, is obtained with photo-catalysis function zirconic acid bismuth
Ceramic glaze.
2. the preparation method according to claim 1 with photo-catalysis function zirconic acid bismuth ceramic glaze, which is characterized in that step
Rapid grinding 2) and in step 3 is carried out in ball grinder, and frit: ball: water quality ratio is 1:1:0.8, milling time 3-5
Hour.
3. the preparation method according to claim 1 with photo-catalysis function zirconic acid bismuth ceramic glaze, which is characterized in that step
It is rapid 4) in glaze slip the mass content of water be 44-50%.
4. the preparation method according to claim 1 with photo-catalysis function zirconic acid bismuth ceramic glaze, which is characterized in that glaze
The mass content of dispersing agent is 0.05-0.15% in slurry.
5. the preparation method according to claim 1 or 4 with photo-catalysis function zirconic acid bismuth ceramic glaze, feature exist
In dispersing agent is sodium carboxymethylcellulose in step 4).
6. the preparation method according to claim 1 with photo-catalysis function zirconic acid bismuth ceramic glaze, which is characterized in that step
Rapid 5) middle use glaze spraying mode carries out glazing.
7. the preparation method according to claim 1 with photo-catalysis function zirconic acid bismuth ceramic glaze, which is characterized in that step
It is rapid 5) in glazing with a thickness of 0.2-0.4mm.
8. the preparation method according to claim 1 with photo-catalysis function zirconic acid bismuth ceramic glaze, which is characterized in that step
It is rapid 5) in dry temperature be 60-80 DEG C.
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