CN106630632A - Preparation method of bismuth zirconate microcrystalline ceramic glaze with photocatalysis function - Google Patents
Preparation method of bismuth zirconate microcrystalline ceramic glaze with photocatalysis function Download PDFInfo
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- CN106630632A CN106630632A CN201611219629.0A CN201611219629A CN106630632A CN 106630632 A CN106630632 A CN 106630632A CN 201611219629 A CN201611219629 A CN 201611219629A CN 106630632 A CN106630632 A CN 106630632A
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- ceramic glaze
- acid bismuth
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- 239000000919 ceramic Substances 0.000 title claims abstract description 50
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 40
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 36
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 25
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000000463 material Substances 0.000 claims abstract description 42
- 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 Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002270 dispersing agent Substances 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 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
- 239000002253 acid Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 11
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 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
- 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 compound [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
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 238000005034 decoration Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract 3
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 239000013078 crystal Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000011222 crystalline ceramic Substances 0.000 description 3
- 229910002106 crystalline ceramic Inorganic materials 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011159 matrix material Substances 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
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000005245 sintering Methods 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
- 238000010521 absorption reaction Methods 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
- 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 230000002708 enhancing effect Effects 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
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 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
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010409 thin film Substances 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Structural Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of bismuth zirconate microcrystalline ceramic glaze with a photocatalysis function. The preparation method comprises the following steps: blending quartz, potassium feldspar, albite, borax, Bi2O3, Suzhou soil and lithium carbonate; preserving heat at 1,270-1,290 DEG C for 20-40min; taking out and pouring into water for quenching to obtain a frit; grinding the frit to obtain a material A; blending the material A with Bi2O3, ZrO2 and Suzhou soil to obtain a material B; adding the material B and a dispersing agent into water, stirring and uniformly mixing to obtain glaze slip; glazing the ceramic surface with the glaze slip; and firing to obtain a bismuth zirconate ceramic glaze with a photocatalysis function. The glaze prepared According to the invention has good gloss and stable chemical property. According to the invention, the ceramic glaze is prepared by adopting a firing technology, coating is not needed, and thus the prepared functional ceramic glaze is tightly combined with a ceramic base and does not fall off easily; and moreover, crystal flowers of special morphology can be quickly formed on the glaze surface, and the surface decoration effect is good.
Description
Technical field
The invention belongs to the technical field of ceramic glaze.It is specifically related to a kind of that there is photo-catalysis function zirconic acid bismuth micro-crystalline ceramic
The preparation method of glaze.
Background technology
Photocatalysis technology is started from 1972, Japanese scholars Fujishima and Honda find on semi-conducting electrode can light urge
Change decomposition water and prepare 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 to the great concern of photocatalysis.With the energy and environmental problem that become increasingly conspicuous,
Rapid development is widely paid attention to and obtained to photocatalysis technology.Catalysis material has degradable organic pollutant, purification empty
The application potential of the aspects such as gas, antibacterial and automatically cleaning.
Because construction sanitary ceramic and domestic ceramics are present in the every aspect of human lives, as modern humans' environmental protection is anticipated
The enhancing of knowledge, for the environmental requirement of ceramic product is also gradually stepped up.Thus, function ceramics enters the visual field of people.Wherein
Just include photocatalysis ceramics.Ceramics with photo-catalysis function, can will be adsorbed in ceramics under conditions of available light irradiation
The organic pollution on surface, bacterium, toxic gas molecular degradation, so as to reach automatically cleaning, antibacterial and the purpose of purify air
[David F Ollis.Photocatalytic purification and remediation ofcontaminated air
and water[J].Chemistry,2000,3:405-411.]。
Photocatalysis ceramics preparation technology is generally divided into 2 classes：One is photochemical catalyst to be added in ceramic glaze, then by generally pottery
Porcelain technique sintering obtains self-cleaning ceramic；Two is that the photochemical catalyst for being coated with one layer of tens nm or hundreds of nm on conventional ceramic surface is thin
Film [Liu Ping, Dai Wenxin, etc. On Photocatalytic Functional Ceramics and its light degradation characteristic [J]. environmental science, 2004,25 (4)：109-
112.].More than method, or poor, the shortcoming of loss easy to fall off that there is photocatalysis film and matrix associativity, or there is photocatalysis
Skewness in agent glaze, exist " rainbow effect " the shortcomings of, directly affect ceramics aesthetic property.
The content 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
Material simultaneously synthesizing photochemical catalyst in preparation process, it is uniform attractive in appearance, it is good with ceramic matrix adhesive force, while photocatalytic degradation is organic
The excellent performance of pollutant, in traditional ceramics field, the surface such as such as building hygiene and domestic ceramics has a wide range of applications.
For achieving the above object, the present invention is adopted the following technical scheme that：
A kind of preparation method with photo-catalysis function zirconic acid bismuth ceramic glaze, comprises the steps：
1) first, 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) enter
Row dispensing；
2) it is the powder after dispensing is dry-mixed and grind, sieve and obtain mixture, by mixture in 1270-1290 DEG C of insulation
20-40min, taking-up is poured into water quenching and frit is obtained；Frit is ground, A material are obtained；
3) by A material and Bi2O3、ZrO2And Suzhou soil is A material according to mass ratio：Bi2O3：ZrO2：Suzhou soil=(82-
86)：(7-7.4)：(2.6-3)：(5-7) proportioning carries out dispensing, and grinding obtains B material；Wherein, Bi2O3With ZrO2Material amount
Ratio meet Bi4Zr3O12In stoichiometric proportion；
4) B material and dispersant are added to the water, stir and evenly mix and be configured to glaze slip；
5) by glaze slip glazing in ceramic surface, Jing roller kilns oxidizing flames burn till after being dried, and firing temperature is 1110-1160
DEG C, firing period total time is 40-50 minutes, and temperature retention time is 6-8 minutes under firing temperature, is obtained with photo-catalysis function zirconium
Sour bismuth ceramic glaze.
The present invention is further improved by, step 2) and step 3 in grind and carried out in ball grinder, and frit：
Ball：Water quality ratio is 1:1:0.8, milling time is 3-5 hours.
The present invention is further improved by, step 4) in glaze slip the mass content of water be 44-50%.
The present invention is further improved by, and the mass content of dispersant is 0.05-0.15% in glaze slip.
The present invention be further improved by, step 4) in dispersant be sodium carboxymethylcellulose.
The present invention be further improved by, step 5) in glazing is carried out using glaze spraying mode.
The present invention be further improved by, step 5) in glazing thickness be 0.2-0.4mm.
The present invention be further improved by, step 5) in be dried temperature be 60-80 DEG C.
The present invention be further improved by, step 5) in firing atmosphere be oxidizing atmosphere.
Compared with prior art, the device have the advantages that：
1. the present invention obtains the ceramic glaze with photo-catalysis function using firing process, and wherein zirconic acid bismuth crystallite component can
To have good intermiscibility with the silicate in biscuit of ceramics, so obtained enamel glossiness is good, stable chemical nature.
2. the present invention prepares ceramic glaze using the technique burnt till, it is not necessary to carry out plated film, so that the function pottery for preparing
Glaze is tightly combined with ceramic matrix, difficult for drop-off, Bi2O3、ZrO2The photochemical catalyst zirconic acid bismuth generated in sintering process exists
It is evenly distributed in glaze, not producing " rainbow effect " affects glaze aesthetic property, and can quickly form special in frit surface
The brilliant flower of the crystallization of pattern, surface decoration effect is good.
3. raw material adopts Suzhou soil, and a small amount of TiO is contained in its composition2, be conducive to lifting the photocatalysis performance of glaze.This
The glaze of bright preparation has photo-catalysis function, and Ceramic glaze can have after 8 hours under illumination condition to organic pollution
There is catalyticing decomposition action, photocatalysis effect test, test result table are carried out to glaze layer using BL-GHX-V type photochemical reaction instrument
The bright resolution ratio to dyestuffs such as rhodamine B and methylene blues can reach 92%.
4. the prepared glaze of the present invention has the spy of the high-transmission rate in the high absorptivity of visible light wave range and to infrared light
Point, photocatalytic ingredient has good visible light-responded.
Description of the drawings
Fig. 1 is the Bi that the glaze layer surface of embodiment 1 is separated out4Zr3O12Crystallite SEM schemes.
Fig. 2 is the glaze layer photocatalytic degradation rhodamine B efficiency chart of embodiment 1.
Specific embodiment
Below in conjunction with the accompanying drawings the present invention is described in detail.
In the present invention in Suzhou soil based on weight/mass percentage composition, containing 37%～39% Al2O3, 46%～48%
SiO2。
Embodiment 1
1) first, by quartz, potassium feldspar, albite, borax, Bi2O3, Suzhou soil, the raw material such as lithium carbonate is according to following quality
Chemical constituent proportioning carries out dispensing.SiO2：Al2O3：B2O3：Bi2O3：Li2O：Na2O：K2O=57：4：22：4：7：4：3.
2) it is above-mentioned powder is dry-mixed and grind, cross 60 mesh sieves and obtain mixture, in being fitted into crucible, it is put into electric furnace 1270
DEG C insulation 20min, taking-up be poured into water quenching be obtained 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, grinding crosses 250 mesh sieves, dry for standby after 3 hours.The powder is designated as A
Material.
3) by above-mentioned A material and Bi2O3、ZrO2And Suzhou soil is A according to mass ratio：Bi2O3：Suzhou soil=82：7.4：7
Proportioning carries out dispensing, and Bi2O3With ZrO2The ratio of amount of material meet Bi4Zr3O12In stoichiometric proportion, be well mixed simultaneously
It is levigate in ball grinder, control material：Ball：Water quality ratio is 1:1:0.8, grinding crosses 250 mesh sieves, dry for standby after 3 hours.The powder
Material is designated as B material.
4) B material and dispersant 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 dispersant is 0.05%, and dispersant is sodium carboxymethylcellulose.
5) adopt the glazing of glaze spraying mode in ceramic surface the above-mentioned glaze slip for preparing, glazing thickness is 0.4mm, at 60 DEG C
Under the conditions of be dried after Jing roller kilns oxidizing flames burn till, firing temperature be 1110 DEG C, firing period be 40 minutes, under firing temperature protect
The warm time is 6 minutes, is obtained with photo-catalysis function zirconic acid bismuth ceramic glaze.
Fig. 1 is the SEM figures that the glaze layer surface prepared under the conditions of embodiment 1 separates out crystallite, 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, its
Middle employing 1000W xenon lamp simulated visible lights, concentration of degrading is the rhodamine B of 3mg/L, and Jing after irradiation in 8 hours, degradation efficiency reaches
92%.
Embodiment 2
1) first, by quartz, potassium feldspar, albite, borax, Bi2O3, Suzhou soil, the raw material such as lithium carbonate is according to following quality
Chemical constituent proportioning carries out dispensing.SiO2：Al2O3：B2O3：Bi2O3：Li2O：Na2O：K2O=58：5：23：3：6：3：2.
2) it is above-mentioned powder is dry-mixed and grind, cross 60 mesh sieves and obtain mixture, in being fitted into crucible, it is put into electric furnace 1280
DEG C insulation 30min, taking-up be poured into water quenching be obtained 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, grinding crosses 250 mesh sieves, dry for standby after 4 hours.The powder is designated as A
Material.
3) by above-mentioned A material and Bi2O3、ZrO2And Suzhou soil is A according to mass ratio：Bi2O3：Suzhou soil=84：7.2：6
Proportioning carries out dispensing, and Bi2O3With ZrO2The ratio of amount of material meet Bi4Zr3O12In stoichiometric proportion, be well mixed simultaneously
It is levigate in ball grinder, control material：Ball：Water quality ratio is 1:1:0.8, grinding crosses 250 mesh sieves, dry for standby after 4 hours.The powder
Material is designated as B material.
4) add water to stir and evenly mix in B material and be configured to glaze slip, the mass content for controlling water is 47%, while adding quality to contain
Measure is 0.10% sodium carboxymethylcellulose as dispersant.
5) adopt the glazing of glaze spraying mode in ceramic surface the above-mentioned glaze slip for preparing, glazing thickness is 0.3mm, at 70 DEG C
Under the conditions of be dried after Jing roller kilns oxidizing flames burn till, firing temperature be 1135 DEG C, firing period be 45 minutes, under firing temperature protect
The warm time is 7 minutes, is obtained with photo-catalysis function zirconic acid bismuth ceramic glaze.
Embodiment 3
1) first, by quartz, potassium feldspar, albite, borax, Bi2O3, Suzhou soil, the raw material such as lithium carbonate is according to following quality
Chemical constituent proportioning carries out dispensing.SiO2：Al2O3：B2O3：Bi2O3：Li2O：Na2O：K2O=59：6：24：2：5：2：1.
2) it is above-mentioned powder is dry-mixed and grind, cross 40 mesh sieves and obtain mixture, in being fitted into crucible, it is put into electric furnace 1290
DEG C insulation 40min, taking-up be poured into water quenching be obtained 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, grinding crosses 250 mesh sieves, dry for standby after 3 hours.The powder is designated as A
Material.
3) by above-mentioned A material and Bi2O3、ZrO2And Suzhou soil is A according to mass ratio：Bi2O3：Suzhou soil=86：7：5 match somebody with somebody
Than carrying out dispensing, and Bi2O3With ZrO2The ratio of amount of material meet Bi4Zr3O12In stoichiometric proportion, be well mixed and in
It is levigate in ball grinder, control material：Ball：Water quality ratio is 1:1:0.8, grinding crosses 250 mesh sieves, dry for standby after 5 hours.The powder
It is designated as B material.
4) B material and dispersant 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 dispersant is 0.15% in glaze slip, and dispersant is sodium carboxymethylcellulose.
5) adopt the glazing of glaze spraying mode in ceramic surface the above-mentioned glaze slip for preparing, glazing thickness is 0.2mm, at 80 DEG C
Under the conditions of be dried after Jing roller kilns oxidizing flames burn till, firing temperature be 1160 DEG C, firing period be 50 minutes, under firing temperature protect
The warm time is 8 minutes, is obtained with photo-catalysis function zirconic acid bismuth ceramic glaze.
The present invention can be realized during prepared by glaze while be directly synthesized the crystallite with photo-catalysis function, can
The problem for effectively overcoming above method to exist.Additionally, because bismuth series photocatalyst has good photocatalysis effect synthesis
Zirconic acid bismuth, except can quickly form the brilliant flower of crystallization with special appearance in frit surface, play good incrustation effect
Really, it is important that with 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 pollutant of the absorption in frit surface.Therefore, from environmental protection
Angle sees, for the innovation of architectural pottery and domestic ceramics, there is huge meaning.
Claims (9)
1. a kind of preparation method with photo-catalysis function zirconic acid bismuth ceramic glaze, it is characterised in that comprise the steps：
1) first, 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) matched somebody with somebody
Material；
2) it is the powder after dispensing is dry-mixed and grind, sieve and obtain mixture, mixture is incubated into 20- at 1270-1290 DEG C
40min, taking-up is poured into water quenching and frit is obtained；Frit is ground, A material are obtained；
3) by A material and Bi2O3、ZrO2And Suzhou soil is A material according to mass ratio：Bi2O3：ZrO2：Suzhou soil=(82-86)：(7-
7.4)：(2.6-3)：(5-7) proportioning carries out dispensing, and grinding obtains B material；Wherein, Bi2O3With ZrO2Material amount ratio expire
Sufficient Bi4Zr3O12In stoichiometric proportion；
4) B material and dispersant are added to the water, stir and evenly mix and be configured to glaze slip；
5) by glaze slip glazing in ceramic surface, Jing roller kilns oxidizing flames burn till after being dried, and firing temperature is 1110-1160 DEG C, is burnt
It it is 40-50 minutes into total time in cycle, temperature retention time is 6-8 minutes under firing temperature, is obtained with photo-catalysis function zirconic acid bismuth
Ceramic glaze.
2. the preparation method with photo-catalysis function zirconic acid bismuth ceramic glaze according to claim 1, it is characterised in that step
It is rapid 2) and to grind and carried out in ball grinder in step 3, and frit：Ball：Water quality ratio is 1:1:0.8, milling time is 3-5
Hour.
3. the preparation method with photo-catalysis function zirconic acid bismuth ceramic glaze according to claim 1, it is characterised in that step
It is rapid 4) in glaze slip the mass content of water be 44-50%.
4. the preparation method with photo-catalysis function zirconic acid bismuth ceramic glaze according to claim 1, it is characterised in that glaze
The mass content of dispersant is 0.05-0.15% in slurry.
5. the preparation method with photo-catalysis function zirconic acid bismuth ceramic glaze according to claim 1 or 4, its feature exists
In step 4) in dispersant be sodium carboxymethylcellulose.
6. the preparation method with photo-catalysis function zirconic acid bismuth ceramic glaze according to claim 1, it is characterised in that step
It is rapid 5) in glazing is carried out using glaze spraying mode.
7. the preparation method with photo-catalysis function zirconic acid bismuth ceramic glaze according to claim 1, it is characterised in that step
It is rapid 5) in glazing thickness be 0.2-0.4mm.
8. the preparation method with photo-catalysis function zirconic acid bismuth ceramic glaze according to claim 1, it is characterised in that step
It is rapid 5) in be dried temperature be 60-80 DEG C.
9. the preparation method with photo-catalysis function zirconic acid bismuth ceramic glaze according to claim 1, it is characterised in that step
It is rapid 5) in firing atmosphere be oxidizing atmosphere.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3819281A1 (en) * | 2019-11-08 | 2021-05-12 | n-tec GmbH | Use of titanium compounds |
| CN113620606A (en) * | 2021-08-12 | 2021-11-09 | 醴陵陶润实业发展有限公司 | Silver metallic luster frit and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001303276A (en) * | 2000-04-28 | 2001-10-31 | Kawasaki Steel Corp | Enamel material |
| CN101067207A (en) * | 2007-06-08 | 2007-11-07 | 东华大学 | Method for producing photo catalytic self-cleaning enamel |
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2016
- 2016-12-26 CN CN201611219629.0A patent/CN106630632B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001303276A (en) * | 2000-04-28 | 2001-10-31 | Kawasaki Steel Corp | Enamel material |
| CN101067207A (en) * | 2007-06-08 | 2007-11-07 | 东华大学 | Method for producing photo catalytic self-cleaning enamel |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3819281A1 (en) * | 2019-11-08 | 2021-05-12 | n-tec GmbH | Use of titanium compounds |
| CN113620606A (en) * | 2021-08-12 | 2021-11-09 | 醴陵陶润实业发展有限公司 | Silver metallic luster frit and preparation method thereof |
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