CN108609849A - A kind of corrosion resistant leadless glaze - Google Patents
A kind of corrosion resistant leadless glaze Download PDFInfo
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- CN108609849A CN108609849A CN201810742144.2A CN201810742144A CN108609849A CN 108609849 A CN108609849 A CN 108609849A CN 201810742144 A CN201810742144 A CN 201810742144A CN 108609849 A CN108609849 A CN 108609849A
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- sericite
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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
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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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Abstract
The invention discloses a kind of corrosion resistant leadless glazes, are related to inorganic non-metallic material（Ceramics）Technical field is made of following component：Barium sulfate, cobaltosic oxide, modified verdelite, active sericite, potassium feldspar, sodium metasilicate, titanium oxide, calcite, strontianite, attapulgite, zinc oxide, boron oxide, silica flour, pigment；Leadless glaze prepared by the present invention can generate the anion of higher concentration after firing；Glaze after leadless glaze prepared by the present invention is fired has good acid-proof alkaline, can effectively prevent loss and destruction of the acid-base property solution to glaze from expanding its application field to improve the performance of glaze.
Description
Technical field
The invention belongs to inorganic non-metallic materials（Ceramics）A kind of technical field, and in particular to corrosion resistant leadless glaze.
Background technology
With the growing tension of traditional energy, scientific and technical development and ceramic process is continuously improved, promotes to make pottery
The production of porcelain develops to high-performance, low energy consumption, inexpensive direction；Color glaze is carried out to ceramic and decorates with a long history, production work
Skill is also highly developed.Refractory ceramics color glaze product is mostly Shi porcelain, and using raw glaze and single firing process, firing temperature exists more
1180~1250 DEG C；Low-temp ceramics color glaze product is mostly fine pottery (including white clouds porcelain), using fritted glaze, using " high temperature biscuiting, low
The firing technique twice of temperature glaze firing ", temperature of glaze firing is generally within the scope of 1000~1080 DEG C;Medium temperature ceramics color glaze product is mostly top grade
Porcelain, using fritted glaze, using firing process twice, temperature of glaze firing is generally 1120~1180 DEG C.Domestic ceramic colour glaze product with
Based on Shi porcelain, supplemented by fine pottery class, it is less that high-grade porcelain products carry out comparing for color glaze decoration.At present, with people's environmental consciousness
Reinforcement, the standard of ceramic product lead-indium alloy is required higher and higher, ceramic containing lead glaze using being decorated not
Adapt to Times ' Demand.It reduces the lead-indium alloy of ceramic, improve product specification, one of most effective measure is exactly to make
It is replaced containing lead glaze with leadless glaze.
After leadless glaze prepared by existing method is fired into finished product, corrosion resistance is general, and glaze is easy to by acid-base property solution
Corrosion, to destroy glaze.
Invention content
The purpose of the present invention is for existing problem, provide a kind of corrosion resistant leadless glaze.
The present invention is achieved by the following technical solutions：
A kind of corrosion resistant leadless glaze, is made of following component by weight：Barium sulfate 3-7, cobaltosic oxide 1.5-1.9,
Modified verdelite 1.2-1.5, active sericite 6-10, potassium feldspar 8-12, sodium metasilicate 10-15, titanium oxide 1-3, calcite 3-6,
Strontianite 2-4, attapulgite 3-6, zinc oxide 5-8, boron oxide 4-6, silica flour 18-22, pigment 0.6-0.8.
Further, the modified verdelite preparation method is：
Tourmaline is broken to 1200 mesh, obtains tourmaline powder, tourmaline is molten in the acylate that mass fraction is 0.5-1.4%
After being impregnated 2 hours in liquid, tourmaline is 70-80g with acylate solution mixed proportion：250mL, then to acylate solution
It is middle add its quality 0.02% rare earth chloride, with 1200r/min rotating speeds stir 2 hours, then filter, using clear water wash to
Neutrality, vacuum drying, obtains modified verdelite.
Further, the acylate solution is maleic acid potassium solution.
Further, the rare earth chloride is yttrium chloride.
Further, the vacuum drying temperature is 52 DEG C.
Further, the active sericite preparation method is：
（1）Sericite is ground, 1800 mesh sieve is crossed, obtains sericite in powder；
（2）Sericite in powder obtained above is pressed into 200-230g：In the weak caustic solution that the mass fraction of 300mL is 2.5%, water-bath
95 DEG C are heated to, the thiocarbamide of sericite in powder quality 1.8% is then added, is stirred 2 hours with 500r/min rotating speeds, was then carried out
Filter, drying to constant weight；
（3）Potassium phosphate is dissolved in prepare in deionized water and obtains the potassium phosphate solution that mass concentration is 25.8%, by potassium phosphate
Solution is heated to 58 DEG C, keeps the temperature 15min, then adds the chloro- 2- hydroxyls of 3- with potassium phosphate equimolar amounts into potassium phosphate solution again
Base propanesulfonate continues to be heated to 72 DEG C, is stirred 2 hours with 500r/min rotating speeds, then ultrasonication 2min, then cools down
It is crystallized to 12 DEG C, continues 40min, then filtering removal crystalline solid, obtains filtrate；The alkane for being 20% by filtrate and mass fraction
Base glycan glycosides aqueous solution, sericite in powder press 300mL：200mL：After the ratio mixing of 80-100g, it is added in reaction kettle, adjusts
Temperature keeps the temperature 10min, then adds 0.1% basic catalyst of sericite in powder quality, be warming up to 88 DEG C to 70 DEG C, with
1200r/min rotating speeds stir 4 hours, are then filtered, are cleaned using deionized water, constant weight are dried under vacuum at 50 DEG C, i.e.,
Obtain active sericite.
Further, the sericite proportion is 2.9g/cm3, volumetric ratio 3.8ml/g.
Further, the weak caustic solution is sodium acetate solution.
Further, the basic catalyst is potassium carbonate.
Lead release（0.1 μ g/ml of detection limit）It is detected, GB/T3534-2002：As a result it is not detected.
Thermal shock resistance, GB/T3298-2008：As a result it does not split.
The present invention has the following advantages compared with prior art：Leadless glaze prepared by the present invention can generate more highly concentrated after firing
The anion of degree；The purposes of anion powder is presented as：(1) purificationization air：Anion in anion powder is in air
Movement is that zigzag is presented.And conveying negative electrical charge is to bacterium, dust, smoke particles and water droplet etc., charge and this this particle
It is combined and is polymerized to ball and sinks, to achieve the purpose that purify air.(2) foreign flavor indoors and various pernicious gases are eliminated：In room
It is remained in the irritative gas such as benzene, formaldehyde, ketone, the ammonia that the art work used during interior decoration evaporates and daily life
Dish leftovers acid smell, cigarette etc. with wall cloth, curtain containing anion powder etc. or contain anion powder to the harmful peculiar smell of people's sheet
Coating, release negative aeroion can effectively be eliminated.(3) health-care effect：Improve cerebral cortex function to keep
The good state of mind；Meanwhile the leadless glaze for preparing of the present invention fire after glaze there is good acid-proof alkaline, Neng Gouyou
Effect prevents loss and destruction of the acid-base property solution to glaze, to improve the performance of glaze, expands its application neck
Domain；Glaze air blister defect after leadless glaze prepared by the present invention is fired significantly reduces, and significantly improves the quality of glaze,
By handling sericite, the active sericite of preparation is added in glaze the present invention, can effectively inhibit bubble
It polymerize and grows up, meanwhile, by the addition of active sericite, the surface tension of glaze can be effectively raised, passes through raising
The surface tension of glaze can rupture after enabling to bubble to generate when bubble reaches glaze in time, simultaneously most importantly,
After bubbles burst, glaze can timely heal with it is smooth, to achieve the effect that prevent air blister defect.
Specific implementation mode
Embodiment 1
A kind of corrosion resistant leadless glaze, is made of following component by weight：Barium sulfate 3, cobaltosic oxide 1.5, modified electricity
Gas stone 1.2, active sericite 6, potassium feldspar 8, sodium metasilicate 10, titanium oxide 1, calcite 3, strontianite 2, attapulgite 3, zinc oxide
5, boron oxide 4, silica flour 18, pigment 0.6.
Further, the modified verdelite preparation method is：
Tourmaline is broken to 1200 mesh, obtains tourmaline powder, by tourmaline in the acylate solution that mass fraction is 0.5%
After impregnating 2 hours, tourmaline is 70g with acylate solution mixed proportion：Then 250mL is added into acylate solution
The rare earth chloride of its quality 0.02% is stirred 2 hours with 1200r/min rotating speeds, then filters, washed to neutrality, very using clear water
Sky is dry, obtains modified verdelite.
Further, the acylate solution is maleic acid potassium solution.
Further, the rare earth chloride is yttrium chloride.
Further, the vacuum drying temperature is 52 DEG C.
Further, the active sericite preparation method is：
（1）Sericite is ground, 1800 mesh sieve is crossed, obtains sericite in powder；
（2）Sericite in powder obtained above is pressed into 200g：In the weak caustic solution that the mass fraction of 300mL is 2.5%, heating water bath
To 95 DEG C, the thiocarbamide of sericite in powder quality 1.8% is then added, is stirred 2 hours with 500r/min rotating speeds, is then filtered, is dried
It does to constant weight；
（3）Potassium phosphate is dissolved in prepare in deionized water and obtains the potassium phosphate solution that mass concentration is 25.8%, by potassium phosphate
Solution is heated to 58 DEG C, keeps the temperature 15min, then adds the chloro- 2- hydroxyls of 3- with potassium phosphate equimolar amounts into potassium phosphate solution again
Base propanesulfonate continues to be heated to 72 DEG C, is stirred 2 hours with 500r/min rotating speeds, then ultrasonication 2min, then cools down
It is crystallized to 12 DEG C, continues 40min, then filtering removal crystalline solid, obtains filtrate；The alkane for being 20% by filtrate and mass fraction
Base glycan glycosides aqueous solution, sericite in powder press 300mL：200mL：After the ratio mixing of 80g, it is added in reaction kettle, adjusts temperature
To 70 DEG C, 10min is kept the temperature, 0.1% basic catalyst of sericite in powder quality is then added, is warming up to 88 DEG C, with
1200r/min rotating speeds stir 4 hours, are then filtered, are cleaned using deionized water, constant weight are dried under vacuum at 50 DEG C, i.e.,
Obtain active sericite.
Further, the sericite proportion is 2.9g/cm3, volumetric ratio 3.8ml/g.
Further, the weak caustic solution is sodium acetate solution.
Further, the basic catalyst is potassium carbonate.
Embodiment 2
A kind of corrosion resistant leadless glaze, is made of following component by weight：Barium sulfate 7, cobaltosic oxide 1.9, modified electricity
Gas stone 1.5, active sericite 10, potassium feldspar 12, sodium metasilicate 15, titanium oxide 3, calcite 6, strontianite 4, attapulgite 6, oxidation
Zinc 8, boron oxide 6, silica flour 22, pigment 0.8.
Further, the modified verdelite preparation method is：
Tourmaline is broken to 1200 mesh, obtains tourmaline powder, by tourmaline in the acylate solution that mass fraction is 1.4%
After impregnating 2 hours, tourmaline is 80g with acylate solution mixed proportion：Then 250mL is added into acylate solution
The rare earth chloride of its quality 0.02% is stirred 2 hours with 1200r/min rotating speeds, then filters, washed to neutrality, very using clear water
Sky is dry, obtains modified verdelite.
Further, the acylate solution is maleic acid potassium solution.
Further, the rare earth chloride is yttrium chloride.
Further, the vacuum drying temperature is 52 DEG C.
Further, the active sericite preparation method is：
（1）Sericite is ground, 1800 mesh sieve is crossed, obtains sericite in powder；
（2）Sericite in powder obtained above is pressed into 230g：In the weak caustic solution that the mass fraction of 300mL is 2.5%, heating water bath
To 95 DEG C, the thiocarbamide of sericite in powder quality 1.8% is then added, is stirred 2 hours with 500r/min rotating speeds, is then filtered, is dried
It does to constant weight；
（3）Potassium phosphate is dissolved in prepare in deionized water and obtains the potassium phosphate solution that mass concentration is 25.8%, by potassium phosphate
Solution is heated to 58 DEG C, keeps the temperature 15min, then adds the chloro- 2- hydroxyls of 3- with potassium phosphate equimolar amounts into potassium phosphate solution again
Base propanesulfonate continues to be heated to 72 DEG C, is stirred 2 hours with 500r/min rotating speeds, then ultrasonication 2min, then cools down
It is crystallized to 12 DEG C, continues 40min, then filtering removal crystalline solid, obtains filtrate；The alkane for being 20% by filtrate and mass fraction
Base glycan glycosides aqueous solution, sericite in powder press 300mL：200mL：After the ratio mixing of 100g, it is added in reaction kettle, adjusts temperature
Degree keeps the temperature 10min, then adds 0.1% basic catalyst of sericite in powder quality, be warming up to 88 DEG C to 70 DEG C, with
1200r/min rotating speeds stir 4 hours, are then filtered, are cleaned using deionized water, constant weight are dried under vacuum at 50 DEG C, i.e.,
Obtain active sericite.
Further, the sericite proportion is 2.9g/cm3, volumetric ratio 3.8ml/g.
Further, the weak caustic solution is sodium acetate solution.
Further, the basic catalyst is potassium carbonate.
Embodiment 3
A kind of corrosion resistant leadless glaze, is made of following component by weight：Barium sulfate 5, cobaltosic oxide 1.6, modified electricity
Gas stone 1.3, active sericite 7, potassium feldspar 10, sodium metasilicate 12, titanium oxide 2, calcite 5, strontianite 3, attapulgite 4, oxidation
Zinc 6, boron oxide 5, silica flour 19, pigment 0.7.
Further, the modified verdelite preparation method is：
Tourmaline is broken to 1200 mesh, obtains tourmaline powder, by tourmaline in the acylate solution that mass fraction is 0.8%
After impregnating 2 hours, tourmaline is 75g with acylate solution mixed proportion：Then 250mL is added into acylate solution
The rare earth chloride of its quality 0.02% is stirred 2 hours with 1200r/min rotating speeds, then filters, washed to neutrality, very using clear water
Sky is dry, obtains modified verdelite.
Further, the acylate solution is maleic acid potassium solution.
Further, the rare earth chloride is yttrium chloride.
Further, the vacuum drying temperature is 52 DEG C.
Further, the active sericite preparation method is：
（1）Sericite is ground, 1800 mesh sieve is crossed, obtains sericite in powder；
（2）Sericite in powder obtained above is pressed into 210g：In the weak caustic solution that the mass fraction of 300mL is 2.5%, heating water bath
To 95 DEG C, the thiocarbamide of sericite in powder quality 1.8% is then added, is stirred 2 hours with 500r/min rotating speeds, is then filtered, is dried
It does to constant weight；
（3）Potassium phosphate is dissolved in prepare in deionized water and obtains the potassium phosphate solution that mass concentration is 25.8%, by potassium phosphate
Solution is heated to 58 DEG C, keeps the temperature 15min, then adds the chloro- 2- hydroxyls of 3- with potassium phosphate equimolar amounts into potassium phosphate solution again
Base propanesulfonate continues to be heated to 72 DEG C, is stirred 2 hours with 500r/min rotating speeds, then ultrasonication 2min, then cools down
It is crystallized to 12 DEG C, continues 40min, then filtering removal crystalline solid, obtains filtrate；The alkane for being 20% by filtrate and mass fraction
Base glycan glycosides aqueous solution, sericite in powder press 300mL：200mL：After the ratio mixing of 90g, it is added in reaction kettle, adjusts temperature
To 70 DEG C, 10min is kept the temperature, 0.1% basic catalyst of sericite in powder quality is then added, is warming up to 88 DEG C, with
1200r/min rotating speeds stir 4 hours, are then filtered, are cleaned using deionized water, constant weight are dried under vacuum at 50 DEG C, i.e.,
Obtain active sericite.
Further, the sericite proportion is 2.9g/cm3, volumetric ratio 3.8ml/g.
Further, the weak caustic solution is sodium acetate solution.
Further, the basic catalyst is potassium carbonate.
Comparative example 1：It is differed only in embodiment 1 and active sericite is replaced with into untreated sericite.
Comparative example 2：Active sericite, which is differed only in, with embodiment 1 replaces with application number：201711073769.6 method
Modified obtained sericite.
Comparative example 3：It is differed only in embodiment 1 and does not add active sericite.
Comparative example 4：The tourmaline that modified verdelite is replaced with to unmodified processing is differed only in embodiment 1.
The bowl biscuit surface of same size is uniformly brushed to the leadless glaze of embodiment and comparative example equivalent, temperature of glaze firing is
1180 DEG C, each group finished product is taken to be placed in seal box, closed 24 hours, with Alphalab companies of the U.S. produce AIC-1000 bear from
Sub- detector is primary every detection in 1 hour, takes 20 data every time, acquires the average value of each data as final detection result,
Test data is shown in Table 1：
Table 1
As can be seen from Table 1, the leadless glaze that prepared by the present invention can generate the anion of higher concentration after firing.
The bowl biscuit surface of same size is uniformly brushed to the leadless glaze of embodiment and comparative example equivalent, temperature of glaze firing is
1180 DEG C, each group finished product is taken to carry out acidproof, alkaline resistance properties：It is detected according to GB/T5003-1999：Acidproof, alkaline resistance properties is A
Grade, and comparative example 1 is acidproof, alkaline resistance properties is C grades, comparative example 2 is acidproof, alkaline resistance properties is B grades.
The biscuit surface of same size is uniformly brushed to the leadless glaze of embodiment and comparative example equivalent, temperature of glaze firing is
1180 DEG C, compare each group glaze：
Table 2
As can be seen from Table 2, the glaze air blister defect after the leadless glaze that prepared by the present invention is fired significantly reduces, and significantly carries
The high quality of glaze.
Claims (9)
1. a kind of corrosion resistant leadless glaze, which is characterized in that be made by weight of following component：Barium sulfate 3-7, four oxidations
Three cobalt 1.5-1.9, modified verdelite 1.2-1.5, active sericite 6-10, potassium feldspar 8-12, sodium metasilicate 10-15, titanium oxide 1-
3, calcite 3-6, strontianite 2-4, attapulgite 3-6, zinc oxide 5-8, boron oxide 4-6, silica flour 18-22, pigment 0.6-
0.8。
2. a kind of corrosion resistant leadless glaze according to claim 1, which is characterized in that the modified verdelite preparation method
For：
Tourmaline is broken to 1200 mesh, obtains tourmaline powder, tourmaline is molten in the acylate that mass fraction is 0.5-1.4%
After being impregnated 2 hours in liquid, tourmaline is 70-80g with acylate solution mixed proportion：250mL, then to acylate solution
It is middle add its quality 0.02% rare earth chloride, with 1200r/min rotating speeds stir 2 hours, then filter, using clear water wash to
Neutrality, vacuum drying, obtains modified verdelite.
3. a kind of corrosion resistant leadless glaze according to claim 2, which is characterized in that the acylate solution is Malaysia
Sour potassium solution.
4. a kind of corrosion resistant leadless glaze according to claim 1, which is characterized in that the rare earth chloride is yttrium chloride.
5. a kind of corrosion resistant leadless glaze according to claim 1, which is characterized in that the vacuum drying temperature is 52
℃。
6. a kind of corrosion resistant leadless glaze according to claim 1, which is characterized in that the activity sericite preparation method
For：
（1）Sericite is ground, 1800 mesh sieve is crossed, obtains sericite in powder；
（2）Sericite in powder obtained above is pressed into 200-230g：In the weak caustic solution that the mass fraction of 300mL is 2.5%, water-bath
95 DEG C are heated to, the thiocarbamide of sericite in powder quality 1.8% is then added, is stirred 2 hours with 500r/min rotating speeds, was then carried out
Filter, drying to constant weight；
（3）Potassium phosphate is dissolved in prepare in deionized water and obtains the potassium phosphate solution that mass concentration is 25.8%, by potassium phosphate
Solution is heated to 58 DEG C, keeps the temperature 15min, then adds the chloro- 2- hydroxyls of 3- with potassium phosphate equimolar amounts into potassium phosphate solution again
Base propanesulfonate continues to be heated to 72 DEG C, is stirred 2 hours with 500r/min rotating speeds, then ultrasonication 2min, then cools down
It is crystallized to 12 DEG C, continues 40min, then filtering removal crystalline solid, obtains filtrate；The alkane for being 20% by filtrate and mass fraction
Base glycan glycosides aqueous solution, sericite in powder press 300mL：200mL：After the ratio mixing of 80-100g, it is added in reaction kettle, adjusts
Temperature keeps the temperature 10min, then adds 0.1% basic catalyst of sericite in powder quality, be warming up to 88 DEG C to 70 DEG C, with
1200r/min rotating speeds stir 4 hours, are then filtered, are cleaned using deionized water, constant weight are dried under vacuum at 50 DEG C, i.e.,
Obtain active sericite.
7. a kind of corrosion resistant leadless glaze according to claim 6, which is characterized in that the sericite proportion is 2.9g/
Cm3, volumetric ratio 3.8ml/g.
8. a kind of corrosion resistant leadless glaze according to claim 6, which is characterized in that the weak caustic solution is that sodium acetate is molten
Liquid.
9. a kind of corrosion resistant leadless glaze according to claim 6, which is characterized in that the basic catalyst is carbonic acid
Potassium.
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| CN201810742144.2A CN108609849A (en) | 2018-07-09 | 2018-07-09 | A kind of corrosion resistant leadless glaze |
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| CN201810742144.2A CN108609849A (en) | 2018-07-09 | 2018-07-09 | A kind of corrosion resistant leadless glaze |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112062470A (en) * | 2020-09-28 | 2020-12-11 | 广东三水大鸿制釉有限公司 | Glaze material and ceramic tile with silk glaze effect and preparation method thereof |
| CN116425518A (en) * | 2021-12-31 | 2023-07-14 | 泉州市德化县恒峰陶瓷有限公司 | Stable-coloring non-color-difference ceramic and preparation method thereof |
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| CN105541410A (en) * | 2016-02-02 | 2016-05-04 | 福建省威尔陶瓷股份有限公司 | Modified tourmaline powder for ceramic glaze, anion ceramic glaze and preparation method |
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2018
- 2018-07-09 CN CN201810742144.2A patent/CN108609849A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105541410A (en) * | 2016-02-02 | 2016-05-04 | 福建省威尔陶瓷股份有限公司 | Modified tourmaline powder for ceramic glaze, anion ceramic glaze and preparation method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112062470A (en) * | 2020-09-28 | 2020-12-11 | 广东三水大鸿制釉有限公司 | Glaze material and ceramic tile with silk glaze effect and preparation method thereof |
| CN116425518A (en) * | 2021-12-31 | 2023-07-14 | 泉州市德化县恒峰陶瓷有限公司 | Stable-coloring non-color-difference ceramic and preparation method thereof |
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Application publication date: 20181002 |
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