CN106673444B - A kind of preparation method with photo-catalysis function zirconic acid yttrium ceramic glaze - Google Patents
A kind of preparation method with photo-catalysis function zirconic acid yttrium ceramic glaze Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/20—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing titanium compounds; containing zirconium compounds
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- 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
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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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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Abstract
A kind of preparation method with photo-catalysis function zirconic acid yttrium ceramic glaze, by quartz, potassium feldspar, albite, borax, Y2O3, 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, and frit is ground to obtain A material；By A material, Y2O3、ZrO2And Suzhou soil ingredient, grinding obtain B material；B material and dispersing agent are added to the water, stirs and evenly mixs and is configured to glaze slip；Glaze slip is fired into ceramic surface with photo-catalysis function zirconic acid yttrium ceramic glaze using the glazing of glaze spraying mode.The present invention prepares ceramic glaze using the technique of firing, does not need to carry out plated film, so that the function ceramics glaze of preparation is tightly combined with ceramic matrix, Y2O3With ZrO2The photochemical catalyst zirconic acid bismuth generated during the sintering process is evenly distributed in glaze, and not generating " rainbow effect " influences glaze aesthetics.
Description
Technical field
The invention belongs to the technical fields of ceramic glaze.There is photo-catalysis function zirconic acid yttrium ceramic glaze more particularly to one kind
Preparation method.
Background technique
21 century, human social development is swift and violent, obtains significant progress in the everyways such as science and technology and economy.However,
The problem of resource and ecology is also outstanding day by day, threatens the sustainable development of human society.The birth of photocatalysis technology, for our benefits
A kind of new thinking is provided with this cleaning of solar energy, cheap, renewable energy.
Photocatalysis technology starts from 1972, discovery [the Fujishima A., Honda of Fujishima-Honda effect
K.Photocatalysis-decomposition of water at the surface of an irradiated
Semiconductor [J] .Nature, 1972,238 (5385): 37-38.], scientific worker is caused to conductor photocatalysis
Greatly concern.And in 1993, Fujishima and Hashimoto are proposed TiO2Photocatalyst applications are in the depollution of environment
Suggestion, cause completely new revolution [Watsunaga T, Hashimoto K, Fujishima A.In Proceeding of
Photocatalytic Purification and Treatment of Water and Air,Amsterdam:
Elsevier,Ollis D F and Al-Ekabi H,1993.].Photocatalysis technology is in sewage treatment, air cleaning and keeps a public place clean
Three fields of degerming are with a wide range of applications.
In recent years, researcher will be with TiO2It is mixed in building materials body or ceramic surface for the photochemical catalyst of representative, has building materials
For the functions such as purification air, sterilization, self-cleaning [Wang Qiang rainbow self-cleaning nona TiO2The preparation of thin-film ceramics is ground with performance
Study carefully the Shanghai [M]: South China Science & Engineering University, 2012:9-12.].This kind of function ceramics can be in sunlight or daylight light irradiation
Under the conditions of, by the organic matter of ceramic surface attachment, bacterium, toxic gas molecular degradation, reach automatically cleaning and purification domestic environment
Effect.
Usual photocatalysis ceramics preparation is divided into 2 classes: first is that photochemical catalyst is added in ceramic glaze, then pressing usual potter
Skill is sintered to obtain self-cleaning ceramic；Second is that thin in the photochemical catalyst that conventional ceramic surface is coated with one layer tens nanometers to several hundred nanometers
[Liu Ping, Dai Wenxin wait On Photocatalytic Functional Ceramics and its light degradation characteristic [J] environmental science, 2004,25 (4): 109- to film
112.].Photochemical catalyst possessed by both the above method is unevenly distributed, and be there is " rainbow effect " or coating and is imitated in conjunction with matrix
The disadvantages of fruit is bad.
Summary of the invention
It is an object of the invention to propose a kind of preparation method with photo-catalysis function zirconic acid yttrium ceramic glaze, this method
The ceramic glaze of preparation both it is good can to cover decorative effect, and have in the purging by crystallization of ceramic surface formation special appearance
Visible light catalytic self-cleaning effect.
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 yttrium ceramic glaze, includes the following steps:
1) firstly, by quartz, potassium feldspar, albite, borax, Y2O3, Suzhou soil, lithium carbonate is according to mass ratio SiO2:
Al2O3: B2O3: Y2O3: Li2O:Na2O:K2O=(57-59): (4-6): (22-24): (2-4): (5-7): (2-4): (1-3) is carried out
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, and frit is ground to obtain A material；
3) by A material, Y2O3、ZrO2And Suzhou soil is A material: Y according to mass ratio2O3: ZrO2: Suzhou soil=(82-86):
(6-8): (2-4): the proportion of (5-7) carries out ingredient, and grinding obtains B material；Wherein, Y2O3With ZrO2Substance amount ratio meet
Y4Zr3O12In 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 is burnt into after ceramic surface, drying through roller kilns oxidizing flame using the glazing of glaze spraying mode, firing temperature
It is 1110-1160 DEG C, firing period is 40-50 minutes, and soaking time is 6-8 minutes under firing temperature, is obtained with photocatalysis
Function zirconic acid yttrium 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 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, Y2O3With ZrO2The photochemical catalyst zirconic acid bismuth generated during the sintering process divides in glaze
Cloth is uniform, and not generating " rainbow effect " influences glaze aesthetics.
2. the photochemical catalyst zirconic acid bismuth generated in the present invention through firing can quickly form special appearance in frit surface
The brilliant flower of crystallization, has good surface decoration effect, and enamel glossiness is good, and chemical property is stablized.
3. raw material uses Suzhou soil, contain a small amount of TiO in ingredient2, be conducive to the absorption benefit for promoting glaze to ultraviolet light
With rate.Glaze prepared by the present invention have photo-catalysis function, Ceramic glaze can under illumination condition after 8 hours to organic
Pollutant has catalyticing decomposition action, carries out photocatalysis effect test to glaze layer using BL-GHX-V type photochemical reactor, surveys
Test result shows that the resolution ratio to dyestuffs such as rhodamine B and methylene blues can achieve 87%.
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 Y that 1 glaze layer surface of embodiment is precipitated4Zr3O12Crystalline substance flower SEM figure.
Fig. 2 is 1 glaze layer photocatalytic degradation rhodamine B efficiency chart of embodiment.
Specific embodiment
Present invention will now be described in detail with reference to the accompanying drawings..
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, Y2O3, Suzhou soil, lithium carbonate is according to following quality chemistry group
Distribution ratio carries out ingredient.SiO2: Al2O3: B2O3: Y2O3: 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) by above-mentioned A material, Y2O3、ZrO2And Suzhou soil is A material: Y according to mass ratio2O3: Suzhou soil=82:8:7 matches
Than carrying out ingredient, and Y2O3With ZrO2The ratio of amount of substance meet Y4Zr3O12In stoichiometric ratio, be uniformly mixed and in ball
Levigate in grinding jar, control material: ball: water quality ratio is 1:1:0.8, crosses 250 meshes after grinding 3 hours, is dried for standby.Powder note
For 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 yttrium ceramic glaze, and opaque effect is good, and has photo-catalysis function.
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
Y4Zr3O12The microscopic appearance of photocatalytic ingredient is that nanometer is linear.Nanowire diameter is about between 40-70nm.
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
87%.
Embodiment 2
1) firstly, by quartz, potassium feldspar, albite, borax, Y2O3, Suzhou soil, lithium carbonate is according to following quality chemistry group
Distribution ratio carries out ingredient.SiO2: Al2O3: B2O3: Y2O3: 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) by above-mentioned A material, Y2O3、ZrO2And Suzhou soil is A material: Y according to mass ratio2O3: Suzhou soil=84:7:6 matches
Than carrying out ingredient, and Y2O3With ZrO2The ratio of amount of substance meet Y4Zr3O12In stoichiometric ratio, be uniformly mixed and in ball
Levigate in grinding jar, control material: ball: water quality ratio is 1:1:0.8, crosses 250 meshes after grinding 4 hours, is dried for standby.Powder note
For 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
47%, the mass content of dispersing agent is 0.10% 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 0.3mm, 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 yttrium ceramic glaze.
Embodiment 3
1) firstly, by quartz, potassium feldspar, albite, borax, Y2O3, Suzhou soil, lithium carbonate is according to following quality chemistry group
Distribution ratio carries out ingredient.SiO2: Al2O3: B2O3: Y2O3: 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) by above-mentioned A material, Y2O3、ZrO2And Suzhou soil is A material: Y according to mass ratio2O3: Suzhou soil=86:6:5 matches
Than carrying out ingredient, and Y2O3With ZrO2The ratio of amount of substance meet Y4Zr3O12In stoichiometric ratio, be uniformly mixed and in ball
Levigate in grinding jar, control material: ball: water quality ratio is 1:1:0.8, crosses 250 meshes after grinding 5 hours, is dried for standby.Powder note
For B material.
4) B material and dispersing agent being added to the water to stir and evenly mix and is configured to glaze slip, the mass content of water is 50% in glaze slip,
The mass content of dispersing agent is 0.15%, 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 yttrium ceramic glaze.
Because zirconic acid yttrium has visible light photocatalysis, this and the common photochemical catalyst with ultraviolet catalytic performance
TiO2It compares, it is higher for natural light utilization efficiency, with more the value of practical application.In addition, the material also has certain fluorescence
Property.So the zirconic acid yttrium of synthesis can also play good surface decoration effect except having self-cleaning effect.Therefore, for building
The innovation for building ceramics and domestic ceramics, there is huge meaning.
Claims (7)
1. a kind of preparation method with photo-catalysis function zirconic acid yttrium ceramic glaze, which comprises the steps of:
1) firstly, by quartz, potassium feldspar, albite, borax, Y2O3, Suzhou soil, lithium carbonate is according to mass ratio SiO2: Al2O3:
B2O3: Y2O3: Li2O:Na2O:K2O=(57-59): (4-6): (22-24): (2-4): (5-7): (2-4): (1-3) carries out ingredient；
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, and frit is ground to obtain A material；
3) by A material, Y2O3、ZrO2And Suzhou soil is A material: Y according to mass ratio2O3: ZrO2: Suzhou soil=(82-86): (6-8):
(2-4): the proportion of (5-7) carries out ingredient, and grinding obtains B material；Wherein, Y2O3With ZrO2The ratio of amount of substance meet Y4Zr3O12
In 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 is burnt into after ceramic surface, drying through roller kilns oxidizing flame using the glazing of glaze spraying mode, firing temperature is
1110-1160 DEG C, firing period is 40-50 minutes, and soaking time is 6-8 minutes under firing temperature, is obtained with photocatalysis function
It can zirconic acid yttrium ceramic glaze.
2. the preparation method according to claim 1 with photo-catalysis function zirconic acid yttrium 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 yttrium 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 yttrium 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 yttrium 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 yttrium ceramic glaze, which is characterized in that step
It is rapid 5) in glazing with a thickness of 0.2-0.4mm.
7. the preparation method according to claim 1 with photo-catalysis function zirconic acid yttrium ceramic glaze, which is characterized in that step
It is rapid 5) in dry temperature be 60-80 DEG C.
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| CN108816214B (en) * | 2018-06-26 | 2021-02-02 | 陕西科技大学 | Bi with full solar spectral response2O2.75/BiO2-xComposite photocatalyst and preparation method and application thereof |
| CN108751717B (en) * | 2018-06-29 | 2021-05-11 | 河源市东源鹰牌陶瓷有限公司 | Anti-slip glaze, anti-slip brick and preparation method thereof |
| CN108842991B (en) * | 2018-06-29 | 2020-06-05 | 佛山石湾鹰牌陶瓷有限公司 | Anti-slip brick and preparation method thereof |
| DE102019007756A1 (en) * | 2019-11-08 | 2021-05-12 | N-Tec Gmbh | Use of titanium compounds |
| CN111620564B (en) * | 2020-05-06 | 2022-03-25 | 佛山科学技术学院 | Luminous glaze with humidity adjusting function |
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| 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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| 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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