CN101255065A - Low-temperature glaze leadless cadmium-free ceramic pigment flux - Google Patents
Low-temperature glaze leadless cadmium-free ceramic pigment flux Download PDFInfo
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- CN101255065A CN101255065A CNA2008100148963A CN200810014896A CN101255065A CN 101255065 A CN101255065 A CN 101255065A CN A2008100148963 A CNA2008100148963 A CN A2008100148963A CN 200810014896 A CN200810014896 A CN 200810014896A CN 101255065 A CN101255065 A CN 101255065A
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Abstract
The invention relates to a lead-and-cadmium-free ceramic pigment flux of low temperature, which is used to produce ceramic pigment for decorative ceramics. The ingredient weight percentages are: 20-40% SiO2, 3-15%SrCO3, 10-30% B2O3, 1-5% Al2O3, 1-5% Na2O, 1-5% K2O, 1-8% Li2CO3, 2-10% ZnO, 1-5% ZrO2, 1-5% SnO2, 0-5% TiO2, 0-5% Ba2CO3, 0-5% CaCO3, 0-5% MgCO3, 1-5% CeO2 and 1-5% Y2O3. The pigment flux of the invention is lead-free, cadmium free, non-toxic, safe and reliable, good in chemical stability and color adaptability, pure in color, colorful, high in gloss and good in quality, low in application temperature, less energy consumption and low in production cost. The flux and pigment are suitable for the traditional crafts methods of screen printing, lithography, spraying, hand-painting and repairing and can be applied in the decoration of a plurality of ceramic products such as hard porcelain, soft porcelain, fine pottery, bone china and vitrified ceramics, particularly suitable for lead-free glazed ceramic decoration.
Description
Technical field
The present invention relates to a kind of improved low-temperature glaze leadless cadmium-free ceramic pigment flux, be made into beramic color and be used for ceramic decoration.
Background technology
Ceramic trailing the most widely is over-glaze decoration, usually, over-glaze decoration all is to use under 750～850 ℃ lesser temps, so need add 30～50% plumbous oxide in traditional production technique so that the barbecue temperature range of colour on glazed ceramics is wide and color development is pure in flux for pigment.As add selenium, cadmium toner and become the indispensable colour system in decorating ceramic products field with the gorgeous color such as bright red, orange, lemon yellow of uniqueness again, but lead, cadmium class beramic color are in production and use, caused that to the pollution of atmosphere, water resources with to the injury of human body common people pay close attention to, especially the lead on tableware, kitchenware surface, cadmium stripping are the potential carcinogenic substances, and people's health is constituted a threat to.For reducing and eradicate the murder by poisoning of heavy metals such as lead, cadmium, unremitting effort is being done always by the scientific research and the production department of ceramic decoration industry both at home and abroad.
Invented a kind of unleaded ceramic pigment flux among the English Patent CB2250285A, its mole percentage composition is: SiO
250～70%, Bi
2O
310～40%, Al
2O
33～30%, B
2O 0～15%, Li
2O 0～10%, Na
2O 0～10%, K
2O 0～10%, MgO 0～5%, CaO 0～10%, ZnO 0～10%, ZrO
20～5%, TiO
20～5%, SnO
20～5%, MoO
30～3%, rare earth 0～3%.
Invented the flux mole percentage composition of unleaded, no cadmium over-glaze pigment: SiO among the Chinese patent CN1044595C
255～80%, Bi
2O
31～8.5%, B
2O
33～15%, Al
2O
31～9%, K
2O 1～9%, Na
2O 0～9%, Li
2O 0～9%, BaO 0～4%, SrO 0～4%, ZrSiO
41.5 SnO～12%,
20.3 La～8.5%,
2O
30～1%, MgO 0～3%, CaO 0～6%, ZnO 0～4%, TiO
20～3%.
These two patents are not difficult to find out from the formation of flux, give the colour on glazed ceramics temperature low, bright characteristics in order to replace plumbous oxide, Cadmium oxide, all application in various degree low-melting Bi
2O
3But bismuth is not only also toxic, and Bi
2O
3Introducing also have following weak point:
1. chemical stability variation:
Bi
2O
3Introducing cause the glass phase-splitting easily, be difficult for to form uniform vitreum, cause the flux short texture, thereby influence chemical stability.Acidproof, alkaline-resisting erosive performance also can descend.
2. Bi
2O
3Add the affiliation cause the toner colour generation impure.
3. thermal expansivity is higher, causes not matching with the coefficient of expansion of ceramic glaze, causes defectives such as " burst porcelains " easily.
4. Bi
2O
3Price higher, cause product cost to increase, influence the market competitiveness.
And the flux adaptability in the existing lead-free cadmium-free ceramic pigment on glaze is relatively poor, and generally speaking, different toners needs the different flux of adapted, and flux is wide in variety, brings great inconvenience to production.
From practice, 750～850 ℃ use temperature is still higher, reduces use temperature, reduces energy consumption, reduces production costs, and also is the target that enterprise is constantly pursued always.
Summary of the invention
The object of the present invention is to provide a kind of low-temperature glaze leadless cadmium-free ceramic pigment flux, the lead-free and cadmium-free nontoxicity, safe and reliable, chemical stability is good again, to the toner wide adaptability, colour generation is pure, and is beautiful in colour, the glossiness height, quality is good, and use temperature is low, and energy consumption is few, and production cost is low.
Low-temperature glaze leadless cadmium-free ceramic pigment flux of the present invention, its ingredients by weight percentage composition is: SiO
220～40%, SrCO
33～15%, B
2O
310～30%, Al
2O
31～5%, Na
2O 1～5%, K
2O 1～5%, Li
2CO
31～8%, ZnO2～10%, ZrO
21～5%, SnO
21～5%, TiO
20～5%, Ba
2CO
30～5%, CaCO
30～5%, MgCO
30～5%, CeO
21～5% and Y
2O
31～5%.
Best group becomes: SiO
225～40%, SrCO
33～8%, B
2O
310～20%, Al
2O
31～5%, Na
2O 1～5%, K
2O 1～5%, Li
2CO
31～8%, ZnO 3～8%, ZrO
21～5%, SnO
21～5%, TiO
20～5%, Ba
2CO
30～5%, CaCO
30～5%, MgCO
30～4%, CeO
21～5% and Y
2O
31～5%.
Identical with common flux preparation method, the desired raw material of buying is mixed in proportion, get final product through 1250～1350 ℃ of temperature fusions, shrend, oven dry.
Flux lead-free and cadmium-free nontoxicity of the present invention, safe and reliable, except that need not the oxide compound of plumbous cadmium, the influence stability that also need not existing domestic and international correlation technique adopted and the expensive Bi of color development
2O
3, only utilize the SiO of the cheapness of some routines
2, SrCO
3, ZrO
2, B
2O
3And rare earth element, the network constituting body of formation even compact, this lays a good foundation to preparation colour generation beramic color pure, that chemical stability is good.Composite fluxing agent by basic metal, alkaline-earth metal and rare earth element are formed when reducing the flux melt temperature, has improved the acid resistance of pigment greatly by mixed alkali effect.The acidic oxide ZrO of macromolecule low bulk
2, TiO
2, SnO
2Not only make the structure of flux tightr with rare earth element etc., and cut down the increase of the caused coefficient of expansion of adding of basic metal and alkaline-earth metal.The every physical and chemical index of the present invention all satisfies international standard.Concrete advantage is as follows:
(1) chemical stability is good, and to the toner wide adaptability, colour generation is pure, and is beautiful in colour, the glossiness height, and quality is good.
In the flux of the present invention, both kept the flux characteristic of potassium, soda metal, by reducing its content, alleviated influence again the toner colour generation.The present invention has adjusted the ratio of alkaline-earth metal in prescription, has added cerium oxide (CeO again
2) and yttrium oxide (Y
2O
3) wait rare earth element, each component cooperatively interacts, interact, the effect of playing stably jointly makes the flux chemical stability after the high temperature melt good, can be widely used in the color development of various toners, be suitable for cobalt chromium system blue-greenish colour, be suitable for cobalt chromium ferromanganese system the grey black look, be suitable for cadmium system reddish yellow, be suitable for the yellow of antimony titanium system, the white etc. that is suitable for the reddish brown brown of iron oxide red system and is suitable for zirconium titanium cerium system, colour generation is pure, does not have obvious aberration, gloss is beautiful, and quality is good.
(2) use temperature is low, and energy consumption is few, and production cost is low.
In the flux of the present invention, adjust the consumption of basic metal and alkaline-earth metal composition, increased Strontium carbonate powder (SrCO
3) and cerium oxide (CeO
2) and yttrium oxide (Y
2O
3) use of rare earth element, increased the meltbility and the transparency of flux, and by reducing silicon-dioxide (SiO
2) and aluminum oxide (Al
2O
3) consumption, thereby the use temperature that makes pigment is reduced to 740～800 ℃ by original 750～850 ℃, has reduced energy consumption, has reduced production cost.And, facts have proved that although reduced use temperature, chemical property, thermostability and the coefficient of expansion of glossiness, colour generation and the acid and alkali-resistance of the pigment that obtains all are better than currently available products, have obtained beyond thought effect.
The toner of toner that uses among the present invention and traditional plumbous cadmium class beramic color is basic identical, no longer repeats, and can directly buy.
The preparation method of low-temperature glaze leadless cadmium-free ceramic pigment flux of the present invention and the pigment directly technology of following conventional lines gets final product, and carries out according to the following step successively:
1. the preparation of flux: the solvent desired raw material of buying is mixed in proportion, through 1250～1350 ℃ of temperature melt water quenchings, dry for standby;
2. ball milling: flux and toner mixing and ball milling to grain diameter＜80 micron, are gone out to grind dry for standby; The weight proportion composition of flux and toner is generally: flux 70%～80%, toner 20%～30%.
3. resintering: compound resintering, shrend under 750～850 ℃ temperature that ball milling is crossed, to increase the density and the vividness of pigment;
4. regrind: the shrend material behind the resintering is reinstalled in the ball mill wet-milling to grain diameter＜5 micron, go out mill, oven dry, pulverize, after testing, granularity, moisture content and form and aspect reach packing warehouse-in after the technical requirements, are the pigment finished product.
The beramic color using method is identical with common product on the glaze of the present invention, can be used for silk screen printing, directly prints or be sprayed at the surface of ceramic, through 740～800 ℃ of barbecues.
After testing, the product physical and chemical index of acquisition is as follows:
1. glossiness: 85-96%.
Utilize the digital glossometer of GM-26D type that color technical institute produces in the Amada Co., Ltd. village to record 45 ° glossiness;
2. thermal expansivity: 40.0-66.0 * 10-
7℃
-1, the 402E type electronic dilatometer that utilizes West Germany to produce records;
3. chemical stability: plumbous quantity of cadmium release is 0.00-0.1mg/dm
2, under 22 ± 2 ℃, soak under 24 hours or 60 ± 2 ℃ 0.5%Na in 4% acetum
2CO
3Soak after 40 hours tone, the equal no change of color and luster in the solution.
Flux of the present invention and pigment are suitable for traditional technology methods such as silk screen printing, planography, spraying, Freehandhand-drawing, repairing; can be applicable to the decoration of multiple ceramics such as hard-paste, soft porcelain, fine earthenware, sclerotin porcelain, vitreous ceramic, be specially adapted to the decoration of leadless glaze pottery.
Embodiment
The invention will be further described below in conjunction with embodiment.
The preparation method of beramic color on the glaze among the embodiment is to prepare burden according to forming, and prepares flux earlier, refabrication pigment, and step is successively:
1. the preparation of flux: in proportion the solvent desired raw material is mixed, through 1300 ± 30 ℃ of temperature melt water quenchings, dry for standby;
2. ball milling: flux and the relevant toner ball milling of packing in proportion is milled to grain diameter＜80 micron, goes out to grind dry for standby;
3. resintering: compound resintering, shrend, oven dry under 800 ± 20 ℃ temperature that ball milling is crossed;
4. regrind: the shrend material behind the resintering is reinstalled in the ball mill wet-milling to grain diameter＜5 micron, the pigment product of go out mill, oven dry, pulverizing.
The composition of beramic color and flux sees Table 1 on the described glaze of the embodiment of the invention.
(continued on next page)
Beramic color and flux ingredients by weight percentage composition table on table 1, the embodiment 1-5 glaze
Each embodiment technical target of the product sees Table 2.
Table 2, embodiment 1-5 technical indicator table
| The barbecue temperature (℃) | Acid and alkali-resistance | Plumbous quantity of cadmium release (mg/dm 2) | The coefficient of expansion (* 10- 7℃ -1) | Glossiness (%) | |
| Embodiment 1 | 800±20 | Soak the back and observe no change | 0 | 53.0 | 88.1 |
| Embodiment 2 | 800±20 | Soak the back and observe no change | 0 | 55.0 | 90.3 |
| Embodiment 3 | 800±20 | Soak the back and observe no change | 0 | 61.0 | 91.3 |
| Embodiment 4 | 800±20 | Soak the back and observe no change | 0 | 51.0 | 88.7 |
| Embodiment 5 | 800±30 | Soak the back and observe no change | 0 | 56.0 | 89.2 |
Claims (2)
1, a kind of low-temperature glaze leadless cadmium-free ceramic pigment flux is characterized in that its ingredients by weight percentage composition is: SiO
220～40%, SrCO
33～15%, B
2O
310～30%, Al
2O
31～5%, Na
2O 1～5%, K
2O 1～5%, Li
2CO
31～8%, ZnO 2～10%, ZrO
21～5%, SnO
21～5%, TiO
20～5%, Ba
2CO
30～5%, CaCO
30～5%, MgCO
30～5%, CeO
21～5% and Y
2O
31～5%.
2, low-temperature glaze leadless cadmium-free ceramic pigment flux according to claim 1 is characterized in that its ingredients by weight percentage composition is: SiO
225～40%, SrCO
33～8%, B
2O
310～20%, Al
2O
31～5%, Na
2O 1～5%, K
2O 1～5%, Li
2CO
31～8%, ZnO 3～8%, ZrO
21～5%, SnO
21～5%, TiO
20～5%, Ba
2CO
30～5%, CaCO
30～5%, MgCO
30～4%, CeO
21～5% and Y
2O
31～5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100148963A CN101255065A (en) | 2008-03-26 | 2008-03-26 | Low-temperature glaze leadless cadmium-free ceramic pigment flux |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100148963A CN101255065A (en) | 2008-03-26 | 2008-03-26 | Low-temperature glaze leadless cadmium-free ceramic pigment flux |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101255065A true CN101255065A (en) | 2008-09-03 |
Family
ID=39890230
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008100148963A Pending CN101255065A (en) | 2008-03-26 | 2008-03-26 | Low-temperature glaze leadless cadmium-free ceramic pigment flux |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101255065A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249736A (en) * | 2011-05-20 | 2011-11-23 | 醴陵陶润实业发展有限公司 | Decoration manufacturing method for forming crystal relief on ceramic plate product |
| CN101607504B (en) * | 2009-07-14 | 2013-01-02 | 深圳市永丰源实业有限公司 | Method for transfer printing of underglaze logo of bone porcelain and transfer printing ink system |
| CN104973784A (en) * | 2015-07-10 | 2015-10-14 | 山东省淄博市博山长虹陶瓷装饰材料厂 | Over-glaze lead-cadmium-free low-temperature ceramic pigment flux |
| CN105461354A (en) * | 2014-09-05 | 2016-04-06 | 广东松发陶瓷股份有限公司 | Domestic porcelain transfer printing lead-free glaze and preparation method thereof |
| CN109437978A (en) * | 2018-11-21 | 2019-03-08 | 朱宝山 | Low-temp ceramics base glaze directly prints glaze ink and its application and ceramic |
| CN110040964A (en) * | 2019-05-13 | 2019-07-23 | 福建省德化县中国白陶瓷有限责任公司 | Clear frit and the method for preparing high white pottery ceramic products thoroughly with it |
| CN111116043A (en) * | 2019-12-30 | 2020-05-08 | 江西新明珠建材有限公司 | 4-level wear-resistant glaze marble tile and manufacturing method thereof |
-
2008
- 2008-03-26 CN CNA2008100148963A patent/CN101255065A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101607504B (en) * | 2009-07-14 | 2013-01-02 | 深圳市永丰源实业有限公司 | Method for transfer printing of underglaze logo of bone porcelain and transfer printing ink system |
| CN102249736A (en) * | 2011-05-20 | 2011-11-23 | 醴陵陶润实业发展有限公司 | Decoration manufacturing method for forming crystal relief on ceramic plate product |
| CN105461354A (en) * | 2014-09-05 | 2016-04-06 | 广东松发陶瓷股份有限公司 | Domestic porcelain transfer printing lead-free glaze and preparation method thereof |
| CN104973784A (en) * | 2015-07-10 | 2015-10-14 | 山东省淄博市博山长虹陶瓷装饰材料厂 | Over-glaze lead-cadmium-free low-temperature ceramic pigment flux |
| CN104973784B (en) * | 2015-07-10 | 2018-03-20 | 山东省淄博市博山长虹陶瓷装饰材料厂 | Lead and cadmium free low-temp ceramics flux for pigment on glaze |
| CN109437978A (en) * | 2018-11-21 | 2019-03-08 | 朱宝山 | Low-temp ceramics base glaze directly prints glaze ink and its application and ceramic |
| CN110040964A (en) * | 2019-05-13 | 2019-07-23 | 福建省德化县中国白陶瓷有限责任公司 | Clear frit and the method for preparing high white pottery ceramic products thoroughly with it |
| CN111116043A (en) * | 2019-12-30 | 2020-05-08 | 江西新明珠建材有限公司 | 4-level wear-resistant glaze marble tile and manufacturing method thereof |
| CN111116043B (en) * | 2019-12-30 | 2022-07-12 | 江西新明珠建材有限公司 | 4-level wear-resistant glaze marble tile and manufacturing method thereof |
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Open date: 20080903 |