CN108585503A - A kind of novel electrostatic prevention ceramic glaze and its preparation method and application - Google Patents
A kind of novel electrostatic prevention ceramic glaze and its preparation method and application 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
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
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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
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/32—Burning methods
- C04B33/34—Burning methods combined with glazing
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- 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
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- 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
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- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
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- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
Abstract
The invention discloses a kind of novel electrostatic prevention ceramic glazes and its preparation method and application, microwave continuous is combined under conventional ceramic clear frit based on raw mineral materials keeps the temperature 20 30 minutes at 1,100 1300 DEG C, carry out quenching is directly poured into water after melting, then frit obtained is placed in ball grinder and is ground, frit powder is obtained after crossing 400 mesh sieve, weighing is carried out by 20 30% mass ratio with the Al-Doped ZnO conductive powder body after the sieve of 150~200 mesh excessively again to mix, the deionized water ball milling mixing of addition 60% is uniform, the performance that sodium carboxymethylcellulose adjusts glaze is added simultaneously, to which glaze slip be made, by slurry obtained it is aging after, it is imposed on using glaze method on dry biscuit of ceramics, it is 3 seconds to soak the glaze time.The ceramic body for having applied glaze is placed on drying in drying box, is sintered later using microwave continuous sintering process.The ceramic glaze glaze that the present invention obtains is smooth, and bubble-free is transparent, and has that chemical stabilization is good, asepsis environment-protecting, it is cheap the advantages that.
Description
Technical field
The present invention relates to ceramic field, more particularly to a kind of novel electrostatic prevention ceramic glaze and its preparation method and application.
Background technology
From the point of view of microstructure, to make glaze conductive, then there must be conductive particle in glaze glass phase, but if conductive
Disperse each other between particle, then can not form conductive path, glaze crucial is a little to make conductive particle with regard to non-conductive
It is connected with each other.Make the connected glass phase melting that must make first in glaze of conductive particle, so that the glass of melting mutually melts a part
Conductive particle, to form flowable conductive melt layer.At high temperature, conductive melt layer mutually expands around with liquid glaze glass
It dissipates and infiltration forms conductive train of thought to which the conductive particle for isolating surrounding connects, when continuous continual conductive train of thought
When being connected on three-dimensional, glaze just has electrical property, the effect of to play antistatic.
Antistatic glaze is typically to be aoxidized by the way that a certain amount of conductive metal system, carbon system and metal are added in common glaze
Object system or compound, then through made from sintering.Metal conductive oxide powder mainly has Fe2O3、TiO2、SnO2, ZnO etc..Anti-
In the production of electrostatic glaze, due to Fe2O3、TiO2The unstable color of performance is deep without large-scale popularization, and SnO2Belong to rare money
Source, using being restricted.Zinc oxide conducting powder has unique advantage as conductive filler.Antistatic glaze mainly by glass phase,
Conductive melt layer and conductive particle composition, conductive melt layer are mutually passed through by permeating and spreading to connect conductive particle in glass
Between matrix, to constitute continuous conductive network.
Clear frit contains two kinds of silica glass network body and boron oxygen network body.Network is more close when containing boron in glaze, from
More difficult by network by electronics, glass-glazed resistance increases.Meanwhile zinc oxide begins to react with boron oxide at 500 DEG C or so
Generate low melting point ZnB2O4(zinc borate), this borate play accelerating agent in fusion process.Therefore zinc oxide is in boracic
There is strong fluxing action, so the present invention selects the glaze of not containing borate as basic glaze in the glaze of ingredient.Together
When melting in view of zinc oxide in Glaze Composition, the AZO conducting powders that the present invention is used for preparing antistatic glaze cross 150~200
Mesh sieve, in addition, zinc oxide since 750 DEG C with the amorphous Si O in glass phase2Reaction generates willemite, and works as silica
In the presence of in the form of quartz, the initial temperature of reaction is to avoid the big of zinc silicate crystalline phase between 1000~1100 DEG C
Amount generates, and Glaze Composition of the invention is based on raw mineral materials.And microwave solid source is a kind of emerging synthesis mode, has and closes
, temperature low, energy conservation and environmental protection the advantages of fast at speed, improves yield after microwave continuous.
Invention content:
It is an object of the invention to overcome the deficiencies of existing technologies, a kind of novel electrostatic prevention ceramic glaze and its preparation side are provided
Method and application.
The present invention uses following technical scheme:
A kind of preparation method of novel electrostatic prevention ceramic glaze, which is characterized in that include the following steps:
(1) microwave continuous is combined under commercially available conventional ceramic clear frit being kept the temperature 20-30 minutes at 1100-1300 DEG C, is melted
It is directly poured into water carry out quenching after melting, obtains frit;
(2) frit obtained is placed in ball grinder and is ground, frit powder is obtained after crossing 300-500 mesh sieve;
(3) it is mixed with Al-Doped ZnO conducting powder, it is uniform that deionized water ball milling mixing is added in mixed powder;
(4) sodium carboxymethylcellulose is added, novel electrostatic prevention ceramic glaze is made.
Preferably, the microwave continuous is combined to, and power is in 3.0-5.0kW.
Preferably, the Al-Doped ZnO conducting powder is the substance by preparing following preparation method:
(1) by ZnO and Al2O3Powder is put into ball grinder, then it is 1 to press the weight ratio of powder, abrading-ball and ethyl alcohol:(1.6-
2):(0.5-1) abrading-ball is added and ethanol solution is disperseed, and ball milling mixing, Ball-milling Time 10-15h are carried out on ball mill;
(2) it is put into drying box, is dried at 100 DEG C after mixing;
(3) by after drying mixed-powder be packed into alumina crucible in, by crucible be placed on microwave continuous be combined in stove into
Row synthesis, synthesis condition are 1200-1300 DEG C, keep the temperature 0.5-1h, obtain conducting powder;
(4) conducting powder that microwave synthesizes is put into ball grinder, is 1 by the weight ratio of conducting powder, abrading-ball:(1.6-2)
It is ground in the ball mill, Ball-milling Time is 1-3 hours, after crossing 150~200 mesh sieve, obtains Al-Doped ZnO conducting powder.
It is further preferred that in the powder, Al2O3Powder content is 1.25-2.50wt%.
Preferably, the dosage of the Al-Doped ZnO conducting powder is the 20-30% of the powder total amount.
Preferably, the synthesis material of the commercially available conventional ceramic clear frit not containing borate.
A kind of novel electrostatic prevention ceramic glaze is made according to the preparation method of any of the above-described.
A kind of application of novel electrostatic prevention ceramic glaze, is used to prepare anti-static ceramic tile.
Preferably, specifically comprise the following steps:
(1) novel electrostatic prevention ceramic glaze slurry is 6-12 hours aging, it is imposed on using glaze method on dry biscuit of ceramics,
It is 3 seconds to soak the glaze time.
(2) ceramic body for having applied glaze is placed on drying in drying box, uses microwave continuous sintering process to carry out later
Sintering.
It is further preferred that step (2) in using microwave continuous sintering process sintering temperature at 1050-1150 DEG C simultaneously
Keep the temperature 0.1-0.25h;Power is in 3.0-5.0kW.
The present invention is using common clear frit available on the market, using raw mineral materials, to prevent ZnO conductive
Powder generates low melting point ZnB with the boric acid reactant salt in raw mineral materials2O4(zinc borate is unfavorable for conduction), so the present invention is to be free of
The glaze of borate is as preferred base glaze.
Sodium carboxymethylcellulose plays the role of adjusting glaze performance, the ceramic green moistened surface of glaze slip and heterogeneity
Situation is different, and rheological property of the glaze slip on the ceramic green surface of heterogeneity is also different, at high temperature the case where dilation
Also different, glaze can be caused to form decorative pattern and even cracked, so, when practical application, will in right amount add according to the case where ceramic green
Enter sodium carboxymethylcellulose to adjust the performance of glaze.
According to the difference (SiO of raw mineral materials main component2Content is in 50-60%) and average grain diameter (nanometer, sub-micron,
Micron), the appropriate power (2-5kW is continuously adjustable) for adjusting microwave controls the rate of heat addition, so as to according to actual conditions preferably
The microwave continuous for implementing conventional ceramic clear frit frit is combined to.
Beneficial effects of the present invention:The ceramic glaze glaze that the present invention obtains is smooth, and bubble-free is transparent, and is had
Chemical stabilization is good, asepsis environment-protecting, it is cheap the advantages that, antistatic glaze surface resistance be 30-180M Ω.
Specific implementation mode
With reference to specific embodiment, the present invention is described in further detail.The conventional ceramic used in embodiment is saturating
Bright glaze, main component SiO2、Al2O3、Fe2O3、TiO2、CaO、MgO、K2O、Na2O、BaO。
Embodiment 1:
The preparation of Al-Doped ZnO conducting powder:
(1) by ZnO and Al2O3Powder is put into ball grinder, wherein Al2O3Powder is the 2.5% of powder total amount, then presses powder
The weight ratio of body, abrading-ball and ethyl alcohol is 1:1.6:1 addition abrading-ball and ethanol solution are disperseed, and ball milling is carried out on ball mill
Mixing, Ball-milling Time 12h;
(2) it is put into drying box, is dried at 100 DEG C after mixing;
(3) by after drying mixed-powder be packed into alumina crucible in, by crucible be placed on microwave continuous be combined in stove into
Row synthesis, microwave power are typically chosen 5kW, and synthesis condition is 1250 DEG C, keeps the temperature 1h, obtains conducting powder;
(4) conducting powder that microwave synthesizes is put into ball grinder, is 1 by the weight ratio of conducting powder, abrading-ball:2 in ball milling
It is ground in machine, Ball-milling Time is 3 hours, after crossing 180 mesh sieve, obtains Al-Doped ZnO conducting powder, conductive powder body resistivity
For 9.8k Ω cm.
The preparation of novel electrostatic prevention ceramic glaze:
(1) microwave continuous is combined under commercially available conventional ceramic clear frit being kept the temperature 30 minutes at 1100 DEG C, and power exists
3.0kW is directly poured into water carry out quenching, obtains frit after melting;
(2) frit obtained is placed in ball grinder and is ground, frit powder is obtained after crossing 500 mesh sieve;
(3) it being mixed with Al-Doped ZnO conducting powder, the dosage of Al-Doped ZnO conducting powder is the 20% of the powder total amount,
The deionized water ball milling mixing of mixed powder addition 60% is uniform;
(4) sodium carboxymethylcellulose is added, novel electrostatic prevention ceramic glaze is made.
Embodiment 2:
The preparation of Al-Doped ZnO conducting powder:
(1) by ZnO and Al2O3Powder is put into ball grinder, wherein Al2O3Powder is the 1.25% of powder total amount, then presses powder
The weight ratio of body, abrading-ball and ethyl alcohol is 1:2:0.5 addition abrading-ball and ethanol solution are disperseed, and ball milling is carried out on ball mill
Mixing, Ball-milling Time 15h;
(2) it is put into drying box, is dried at 100 DEG C after mixing;
(3) by after drying mixed-powder be packed into alumina crucible in, by crucible be placed on microwave continuous be combined in stove into
Row synthesis, microwave power are typically chosen 3kW, and synthesis condition is 1300 DEG C, keeps the temperature 0.5h, obtains conducting powder;
(4) conducting powder that microwave synthesizes is put into ball grinder, is 1 by the weight ratio of conducting powder, abrading-ball:1.8 in ball
It is ground in grinding machine, Ball-milling Time is 2 hours, after crossing 200 mesh sieve, obtains Al-Doped ZnO conducting powder, conductive powder body resistance
Rate is 5.8k Ω cm.
The preparation of novel electrostatic prevention ceramic glaze:
(1) microwave continuous is combined under commercially available conventional ceramic clear frit being kept the temperature 20 minutes at 1300 DEG C, and power exists
5.0kW is directly poured into water carry out quenching, obtains frit after melting;
(2) frit obtained is placed in ball grinder and is ground, frit powder is obtained after crossing 300 mesh sieve;
(3) it being mixed with Al-Doped ZnO conducting powder, the dosage of Al-Doped ZnO conducting powder is the 30% of the powder total amount,
The deionized water ball milling mixing that mixed powder is added to system 60% is uniform;
(4) sodium carboxymethylcellulose is added, novel electrostatic prevention ceramic glaze is made.
Embodiment 3:
The preparation of Al-Doped ZnO conducting powder:
(1) by ZnO and Al2O3Powder is put into ball grinder, wherein Al2O3Powder is the 2.0% of powder total amount, then presses powder
The weight ratio of body, abrading-ball and ethyl alcohol is 1:1.8:0.8 addition abrading-ball and ethanol solution are disperseed, and ball is carried out on ball mill
Mill mixing, Ball-milling Time 10h;
(2) it is put into drying box, is dried at 100 DEG C after mixing;
(3) by after drying mixed-powder be packed into alumina crucible in, by crucible be placed on microwave continuous be combined in stove into
Row synthesis, microwave power are typically chosen 1kW, and synthesis condition is 1200 DEG C, keeps the temperature 0.8h, obtains conducting powder;
(4) conducting powder that microwave synthesizes is put into ball grinder, is 1 by the weight ratio of conducting powder, abrading-ball:1.6 in ball
It is ground in grinding machine, Ball-milling Time is 1 hour, after crossing 150 mesh sieve, obtains Al-Doped ZnO conducting powder, conductive powder body resistance
Rate is 3.0k Ω cm.
The preparation of novel electrostatic prevention ceramic glaze:
(1) microwave continuous is combined under commercially available conventional ceramic clear frit being kept the temperature 25 minutes at 1200 DEG C, and power exists
4.0kW is directly poured into water carry out quenching, obtains frit after melting;
(2) frit obtained is placed in ball grinder and is ground, frit powder is obtained after crossing 400 mesh sieve;
(3) it being mixed with Al-Doped ZnO conducting powder, the dosage of Al-Doped ZnO conducting powder is the 26% of the powder total amount,
The deionized water ball milling mixing that mixed powder is added to system 60% is uniform;
(4) sodium carboxymethylcellulose is added, novel electrostatic prevention ceramic glaze is made.
Embodiment 4:
The application of novel electrostatic prevention ceramic glaze prepared by embodiment 1:
(1) aging 6 hours of the novel electrostatic prevention ceramic slurry prepared embodiment 1, dry pottery is imposed on using glaze method
On porcelain biscuit, the leaching glaze time is 3 seconds.
(2) ceramic body for having applied glaze is placed on drying in drying box, uses microwave continuous sintering process to carry out later
Sintering, sintering temperature is at 1050 DEG C and keeps the temperature 0.1h;Power is in 4.0kW.
Obtained antistatic glaze surface resistance is 180M Ω.
Embodiment 5:
The application of novel electrostatic prevention ceramic glaze prepared by embodiment 1:
(1) aging 10 hours of the novel electrostatic prevention ceramic slurry prepared embodiment 1, dry pottery is imposed on using glaze method
On porcelain biscuit, the leaching glaze time is 3 seconds.
(2) ceramic body for having applied glaze is placed on drying in drying box, uses microwave continuous sintering process to carry out later
Sintering, sintering temperature is at 1150 DEG C and keeps the temperature 0.15h;Power is in 3.0kW.
Obtained antistatic glaze surface resistance is 90M Ω.
Embodiment 6:
The application of novel electrostatic prevention ceramic glaze prepared by embodiment 1:
(1) aging 12 hours of the novel electrostatic prevention ceramic slurry prepared embodiment 1, dry pottery is imposed on using glaze method
On porcelain biscuit, the leaching glaze time is 3 seconds.
(2) ceramic body for having applied glaze is placed on drying in drying box, uses microwave continuous sintering process to carry out later
Sintering, sintering temperature is at 1100 DEG C and keeps the temperature 0.25h;Power is in 5.0kW.
Obtained antistatic glaze surface resistance is 30M Ω.
Above-described embodiment is merely illustrative of the technical solution of the present invention and is not intended to limit it, all without departing from the present invention
Any modification of spirit and scope or equivalent replacement should all cover the range in technical solution of the present invention.
Claims (10)
1. a kind of preparation method of novel electrostatic prevention ceramic glaze, which is characterized in that include the following steps:
(1) microwave continuous is combined under commercially available conventional ceramic clear frit being kept the temperature 20-30 minutes at 1100-1300 DEG C, after melting
It directly is poured into water carry out quenching, obtains frit;
(2) frit obtained is placed in ball grinder and is ground, frit powder is obtained after crossing 300-500 mesh sieve;
(3) it is mixed with Al-Doped ZnO conducting powder, it is uniform that deionized water ball milling mixing is added in mixed powder;
(4) sodium carboxymethylcellulose is added, novel electrostatic prevention ceramic glaze is made.
2. a kind of preparation method of novel electrostatic prevention ceramic glaze according to claim 1, which is characterized in that the microwave
It is continuously synthesizing to, power is in 3.0-5.0kW.
3. a kind of preparation method of novel electrostatic prevention ceramic glaze according to claim 1, which is characterized in that described to mix alumina
It is the substance by preparing following preparation method to change zinc conducting powder:
(1) by ZnO and Al2O3Powder is put into ball grinder, then it is 1 to press the weight ratio of powder, abrading-ball and ethyl alcohol:(1.6-2):
(0.5-1) abrading-ball is added and ethanol solution is disperseed, and ball milling mixing, Ball-milling Time 10-15h are carried out on ball mill;
(2) it is put into drying box, is dried at 100 DEG C after mixing;
(3) mixed-powder after drying is packed into alumina crucible, crucible is placed on microwave continuous and is combined to close in stove
At synthesis condition is 1200-1300 DEG C, keeps the temperature 0.5-1h, obtains conducting powder;
(4) conducting powder that microwave synthesizes is put into ball grinder, is 1 by the weight ratio of conducting powder, abrading-ball:(1.6-2) is in ball
It is ground in grinding machine, Ball-milling Time is 1-3 hours, after crossing 150~200 mesh sieve, obtains Al-Doped ZnO conducting powder.
4. a kind of preparation method of novel electrostatic prevention ceramic glaze according to claim 3, which is characterized in that the powder
In, Al2O3Powder content is 1.25-2.50wt%.
5. a kind of preparation method of novel electrostatic prevention ceramic glaze according to claim 1, which is characterized in that described to mix alumina
The dosage for changing zinc conducting powder is the 20-30% of the powder total amount.
6. a kind of preparation method of novel electrostatic prevention ceramic glaze according to claim 1, which is characterized in that described commercially available general
The synthesis material of logical ceramics clear frit not containing borate.
7. a kind of novel electrostatic prevention ceramic glaze, which is characterized in that novel electrostatic prevention ceramic glaze is according to any one of claim 1-4
Preparation method be made.
8. a kind of application of novel electrostatic prevention ceramic glaze, which is characterized in that be used to prepare anti-static ceramic tile.
9. a kind of application of novel electrostatic prevention ceramic glaze according to claim 8, which is characterized in that concrete application method is such as
Under:
(1) novel electrostatic prevention ceramic glaze slurry is 6-12 hours aging, it is imposed on using glaze method on dry biscuit of ceramics, soaks glaze
Time is 3 seconds.
(2) ceramic body for having applied glaze is placed on drying in drying box, is sintered later using microwave continuous sintering process.
10. a kind of application of novel electrostatic prevention ceramic glaze according to claim 9, which is characterized in that used in step (2)
The sintering temperature of microwave continuous sintering process is at 1050-1150 DEG C and keeps the temperature 0.1-0.25h;Power is in 3.0-5.0kW.
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