CN1021112C - Low-temp. ceramic glazing dyestuff and its preparation method - Google Patents
Low-temp. ceramic glazing dyestuff and its preparation method Download PDFInfo
- Publication number
- CN1021112C CN1021112C CN 89106845 CN89106845A CN1021112C CN 1021112 C CN1021112 C CN 1021112C CN 89106845 CN89106845 CN 89106845 CN 89106845 A CN89106845 A CN 89106845A CN 1021112 C CN1021112 C CN 1021112C
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- China
- Prior art keywords
- flux
- preparation
- ceramic
- sno
- colour
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/04—Opacifiers, e.g. fluorides or phosphates; Pigments
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The present invention relates to low temperature ceramic glazing pigment, which is characterized in that the fluxing agent is composed of a host fluxing agent, a compounding fluxing agent and a stabilizing agent, wherein the host fluxing agent is composed of PbO, B2O3, SiO2 and Al2O3, the compounding fluxing agent is composed of Li2O, Na2O, K2O and NgO, and the stabilizing agent is selected from ZrO2, TiO2, SnO2 and ZnO. The low temperature ceramic glazing pigment has the roasting temperature of 680 to 800 DEG C, the glossiness of 68 to 78%, good chemical stability and suitable expansion coefficient, and thus, the low temperature ceramic glazing pigment can be used as the decorations for various ceramic articles, such as hard ceramic, stoneware, fine ceramic, bone ceramic, vitreous ceramic, etc. The low temperature ceramic glazing pigment can be also used as the decorations for enamelware and simultaneously as the decorations for wire meshes and planographic printings.
Description
The present invention relates to a kind of low-temp ceramics over-glaze pigment and preparation method thereof, belong to beramic color, it comprises toner and flux.
Obtain the low and wide ranges of a kind of roasting burning temperature, the glossiness height, solidity to corrosion is strong, is desirable and have the broad-spectrum colour on glazed ceramics of the suitable coefficient of expansion, and the ceramic industry worker of countries such as China, the Soviet Union, Japan, West Germany, Britain is doing unremitting effort always for this reason.Disclose a kind of flux that is used for colour on glazed ceramics in russian patent SU-1435553, its purpose is to reduce the melt temperature of pigment, and its composition is (mol%) SiO
251.47～52.27; PbO6.94～8.17; Al
2O
35.79～5.91; B
2O
311.97～12.17; ZnO7.30～7.37; CaO6.58～6.68; Na
2O2.38～2.40; Fe
2O
30.09～0.16MgO0.43～0.48; ZrO
25.71～5.74; Glossiness is 61～63%.Weak point is the still higher and narrow range of melt temperature, and glossiness is also undesirable.
The objective of the invention is to overcome above-mentioned the deficiencies in the prior art part and provide a kind of melt temperature low and wide ranges, the glossiness height, resistance to chemical corrosion is good, has the suitable coefficient of expansion, performance of technical process is good, and use range is colour on glazed ceramics and preparation method thereof widely.
Purpose of the present invention can reach by following measure: pigment is made up of the flux of 70～95% weight and the toner of 5～30% weight, wherein flux be by 64.5～94.6mol% by PbO, B
2O
3, SiO
2, Al
2O
3The composite fluxing agent that main body flux of forming and oxide compound or the salt by basic metal and alkaline-earth metal of 4.0～16.1mol% are formed and 1.4～4.5mol% are by SnO
2With from ZrO
2, TiO
2, stablizer three parts formed of the component that chooses among the ZnO form.
Purpose of the present invention can also reach by following measure: the compositing range of main body flux is (mol%): PbO10.0～26.0 in the flux; B
2O
33.5～15.0; SiO
248.0～60.0Al
2O
33.0～7.0.The compositing range of the composite fluxing agent in the flux is (mol%): Li
2O1.5～4.2; Na
2O1.5～5.9; K
2O0.5～3.0; MgO0.5～5.0.The compositing range of the stablizer in the flux is (mol%): SnO
20.2～1.8; TiO
20～1.0; ZrO
20～1.7; ZnO0～2.0.
In view of the difference of other pigment performances beyond selenium, cadmium dye and the selenium cadmium class, we have developed optimal prescription respectively.The desirable compositing range that is suitable for Cadmium Sulfide and sulphur westernization cadmium dye is (mol%) PbO10.0～15.0; B
2O
310.0～15.0; SiO
250.0～60.0; Al
2O
33.0～6.0; Li
2O2.0～4.0; Na
2O2.0～4.0; K
2O0.5～3.0; MgO0.5～1.0; ZrO
21.5～1.7; TiO
2, 0.4～0.5; SnO
20.2～1.8.
The preferred version compositing range that is suitable for selenium-cadmium dye other colour on glazed ceramicss in addition is (mol%): PbO15.0～25.0; B
2O
33.5～15.0; SiO
248.0～58.0; Al
2O
33.0～7.0; Li
2O1.5～4.2; Na
2O1.5～5.9; K
2O0.5～3.0; MgO1.5～5.0; SnO
20.2～1.8; ZnO1.2～2.0.
Each component in the above-mentioned prescription is promptly showing own inherent function, plays a part again between the each component to remedy mutually, replenishes mutually, has reached an ideal purpose jointly.
Aforementioned body flux is the skeleton of flux, is as the indispensable component of the flux of beramic color, and what of its content play crucial effect to the character of flux, and in order to reduce the temperature of fusion of pigment, we have selected strong fusing assistant Li for use
2O, but singly add Li
2Though O can reduce the roasting temperature of burning, reduced the chemical stability of pigment simultaneously, and colour generation is not just yet.For this reason, we add the oxide compound or the salt of basic metal and alkaline-earth metal simultaneously and make composite fluxing agent, and have avoided independent use Li
2The side effect of O has produced and has not only reduced the barbecue temperature but also the roasting good result of burning temperature range of broad is arranged.
Stablizer SnO of the present invention
2And ZrO
2, TiO
2Or the adding of ZnO both reduced the coefficient of expansion, improved the chemical stability of pigment again, thus to obtain high against corrosion, have the suitable coefficient of expansion again and increase greatly with ceramic sticking power aspect and have outstanding effect.
The raising of pigment gloss degree of the present invention and the improvement of over-all properties are to lean on the appropriateness of whole prescription to realize.
The preparation method of low-temp ceramics over-glaze pigment of the present invention is: with the toner mixing and ball milling of the flux of 70～95% weight and 5～30% weight to fineness 10 μ m, in 750～800 ℃ of resinterings, shrend, again in ball mill wet-milling to the fineness 5 μ m, oven dry, crushing packing then.Wet grinding media is water or alcohol, preferably alcohol.
The preparation method of the toner in the above-mentioned method for preparing pigment is that oven dry was calcined down for → 600～1350 ℃ and formed under weigh batching → wet ball grinding mixed → 100～120 ℃.
The preparation method of flux is in the above-mentioned method for preparing pigment: weigh batching → dry mixed → 1250 ℃～1320 ℃ of following fusion → shrend → oven dry form.
Embodiment
Table I table II
The present invention has following advantage compared to existing technology:
1, the grilling temperature is low and temperature range is wide, 680～800 ℃. Not only the grilling energy 20% can be saved, and the grilling yield rate can be improved.
2, glossiness height, 68～78%.
3, hot expansibility is suitable, can be used for the decoration of various ceramic blank glaze, " burst porcelain " phenomenon can not occur.
4, chemical stability is good.
(1) in 4% acetum, under 22 ± 2 ℃ of temperature, soaked 24 hours, with stripping quantity PPM value plumbous in the atomic absorption spectrophotometer acetic acid soak, cadmium, Pb=0.05～0.30mg/dm2，Cd＝0.03～0.08mg/dm
2。
(2) in 4% acetum, under 22 ± 2 ℃ of temperature, soaked 24 hours, wash airing, it is unchanged to observe color harmony gloss.
(3) at 0.5% Na2CO
3In the solution, soaked 32 hours under 60 ± 2 ℃ of temperature, wash airing, it is unchanged to observe hue and luminance.
5, Technological adaptability is good, is applicable to the processes such as screen printing, lithographic printing, aerograph, Freehandhand-drawing, repairing.
6, the scope of application is wide, can be used for the decoration of the multiple ceramics such as hard-paste, soft-paste, Shi porcelain, fine earthenware, bone china and vitreous ceramic. Simultaneously, the decoration that also can be used for enamelware.
Claims (7)
1, a kind of colour on glazed ceramics comprises flux and toner, it is characterized in that being made up of the flux of 70～95% weight and the toner of 5～30% weight, and flux comprises (mol%):
A: main body flux 64.5～94.6
Wherein: PbO 10.0～26.0
B
2O
33.5～15.0
SiO
248.0～60.0
Al
2O
33.0～7.0
B: composite fluxing agent 4.0～16.1
Wherein: Li
2O 1.5～4.2
Na
2O 1.5～5.9
K
2O 0.5～3.0
MgO 0.5～5.0
C: stablizer 1.4～4.5
Wherein: SnO
2Be neccessary composition, from TiO
2, ZrO
2, select among the ZnO a kind ofly at least, its compositing range is:
SnO
20.2～1.8
TiO
20～1.0
ZrO
20～1.7
ZnO
20～2.0
2, according to the described colour on glazed ceramics of claim 1, the flux compositing range that it is characterized in that being suitable for Cadmium Sulfide and cadmium sulfoselenide class pigment is (mol%)
PbO 10.0～15.0
B
2O
310.0～15.0
SiO
250.0～60.0
Al
2O
33.0～6.0
Li
2O 2.0～4.0
Na
2O 2.0～4.0
K
2O 0.5～3.0
MgO 0.5～1.0
ZrO
21.5～1.7
TiO
20.3～0.5
SnO
20.2～1.8
3, according to the described colour on glazed ceramics of claim 1, the flux compositing range that it is characterized in that being suitable for other colour on glazed ceramicss beyond the selenium-cadmium dye is (mol%):
PbO 15.0～25.0
B
2O
33.5～15.0
SiO
248.0～58.0
Al
2O
33.0～7.0
Li
2O 1.5～4.2
Na
2O 1.5～5.9
K
2O 0.5～3.0
MgO 1.5～5.0
SnO
20.2～1.8
ZnO 1.2～2.0
4, according to the described colour on glazed ceramics of claim 1, it is characterized in that the preparation method is that toner mixing and ball milling with the flux of 70～95% weight and 5～30% weight is to fineness 10 μ m, in 750～800 ℃ of resinterings, shrend, again in ball mill wet-milling to the fineness 5 μ m, oven dry, crushing packing then.
5,, it is characterized in that wet grinding media is water or alcohol, preferably alcohol according to the described preparation method of claim 4.
6, according to the described colour on glazed ceramics of claim 1, it is characterized in that the preparation method of toner is: ℃ following calcining of weigh batching → wet ball grinding mixing → oven dry → 600～1350 forms.
7, according to the described colour on glazed ceramics of claim 1, it is characterized in that the preparation method of flux is: weigh batching → dry mixed → 1250 ℃～1320 ℃ of following fusion → shrend → oven dry form.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89106845 CN1021112C (en) | 1989-10-25 | 1989-10-25 | Low-temp. ceramic glazing dyestuff and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89106845 CN1021112C (en) | 1989-10-25 | 1989-10-25 | Low-temp. ceramic glazing dyestuff and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1042698A CN1042698A (en) | 1990-06-06 |
| CN1021112C true CN1021112C (en) | 1993-06-09 |
Family
ID=4856918
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89106845 Expired - Lifetime CN1021112C (en) | 1989-10-25 | 1989-10-25 | Low-temp. ceramic glazing dyestuff and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1021112C (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1044595C (en) * | 1994-11-17 | 1999-08-11 | 山东省硅酸盐研究设计院 | Leadless cadmiumless ceramic glazing pigment |
| CN100363306C (en) * | 2005-11-15 | 2008-01-23 | 毛海燕 | Crystal diffusion drying granule for ceramic product and preparation process thereof |
| CN101050059B (en) * | 2007-05-15 | 2010-05-19 | 淄博华为颜料有限公司 | Covering layer without lead, cadmium of pigment without lead on ceramic glaze, and preparation method |
| EP2000443B1 (en) * | 2007-05-29 | 2012-08-22 | Sociedad Anónima Minera Catalano-Aragonesa | Metallic glaze composition |
| CN102627478B (en) * | 2012-04-28 | 2014-02-05 | 湖南金环颜料有限公司 | Method for preparing yellow pigment by using commonly used color development for replacing rare-earth element praseodymium and vanadium color development |
| CN102731157B (en) * | 2012-06-14 | 2013-11-20 | 卡罗比亚釉料（昆山）有限公司 | Lead-containing assistant of frit used for preparation of ceramics |
| CN107032611A (en) * | 2016-11-05 | 2017-08-11 | 江苏省宜兴彩陶工艺厂 | Easy fired crab green glaze and preparation method thereof |
| CN107793033A (en) * | 2017-11-06 | 2018-03-13 | 江苏宜翔陶瓷科技有限公司 | Suitable for the sapphire blue glaze repeatedly to flash back |
| CN116282924B (en) * | 2023-03-28 | 2024-08-09 | 邯郸市槐山新材料科技有限公司 | Low-temperature porcelain glaze composition and preparation method and application thereof |
-
1989
- 1989-10-25 CN CN 89106845 patent/CN1021112C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1042698A (en) | 1990-06-06 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| C10 | Entry into substantive examination | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
| OR01 | Other related matters | ||
| ASS | Succession or assignment of patent right |
Owner name: ZIBO FULU NEW MATERIAL CO., LTD. Free format text: FORMER OWNER: SHANDONG GUIYUAN NEW MATERIALS SCIENCE CO., LTD. Effective date: 20070406 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| C56 | Change in the name or address of the patentee |
Owner name: SHANDONG GUIYUAN NEW MATERIALS SCIENCE CO., LTD. Free format text: FORMER NAME OR ADDRESS: SILICATE RESEARCH AND DESIGN INST., SHANDONG PROV. |
|
| CP03 | Change of name, title or address |
Address after: 255086 Shandong province high tech Industrial Development Zone of Zibo Willow Road No. 264 Patentee after: Shandong Silicon Garden New Material Technology Co.,Ltd. Address before: 255129, No. 163 West Railway, Zibo, Shandong, Kunlun Patentee before: Shandong Silicate Research and Design Institute |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20070406 Address after: 255100 No. 263 Railway Street, Kunlun Town, Zichuan District, Shandong, Zibo Patentee after: Zibo Fulu new material LLC Address before: 255086 Shandong province high tech Industrial Development Zone of Zibo Willow Road No. 264 Patentee before: Shandong Silicon Garden New Material Technology Co.,Ltd. |
|
| C17 | Cessation of patent right | ||
| CX01 | Expiry of patent term |
Granted publication date: 19930609 |