CN1042698A - Low-temp ceramics over-glaze pigment and preparation method thereof - Google Patents

Low-temp ceramics over-glaze pigment and preparation method thereof Download PDF

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Publication number
CN1042698A
CN1042698A CN 89106845 CN89106845A CN1042698A CN 1042698 A CN1042698 A CN 1042698A CN 89106845 CN89106845 CN 89106845 CN 89106845 A CN89106845 A CN 89106845A CN 1042698 A CN1042698 A CN 1042698A
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flux
mol
pbo
sno
sio
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CN 89106845
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CN1021112C (en
Inventor
张道学
殷书建
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Shandong Silicon Garden New Material Technology Co ltd
Zibo Fulu New Material LLC
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Shandong silicate research and design institute
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Priority to CN 89106845 priority Critical patent/CN1021112C/en
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Publication of CN1021112C publication Critical patent/CN1021112C/en
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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
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/04—Opacifiers, e.g. fluorides or phosphates; Pigments

Abstract

The present invention is a kind of low-temp ceramics over-glaze pigment, it is characterized in that flux is by PbO, B 2O 3, SiO 2, Al 2O 3The main body flux of forming and by Li 2O, Na 2O, K 2The composite fluxing agent that O, MgO form and from ZrO 2, TiO 2, SnO 2, the stablizer that chooses among the ZnO forms.Roasting 680～800 ℃ of the temperature of burning; Glossiness 68～78%; Chemical stability is good and the suitable coefficient of expansion is arranged, and can be used for the decoration of multiple ceramics such as hard-paste, stoneware, fine earthenware, bone china and vitreous ceramic, also can be used for the decoration of enamelware, also is suitable for silk screen and flat stamping simultaneously and decorates.

Description

Low-temp ceramics over-glaze pigment and preparation method thereof
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, and to have the broad-spectrum colour on glazed ceramics of the suitable coefficient of expansion be desirable, 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: (wt%) SiO 236.94～39.34; PbO 18.0～23.0; Al 2O 37.02～7.48; B 2O 39.87～10.51; ZnO 7.01～7.45; CaO 4.38～4.67; Na 2O 1.76～1.87; Fe 2O 30.22～0.24; MgO 0.22～0.24; ZrO 28.26～8.80.The melt temperature of flux is 750～800 ℃; 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 weak point of the prior art 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 4.6～16.1mol% are formed and 1.4～4.5mol% 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%): PbO 10.0～26.0 in the flux; B 2O 33.5～15.0; SiO 248.0～60.0; Al 2O 33.0～7.0.The compositing range of the composite fluxing agent in the flux is (mol%): Li 2O 1.5～4.2; Na 2O 1.5～5.9; K 2O 0.5～1.0; MgO 0.5～5.0.The compositing range of the stablizer in the flux is (mol%): SnO 20.2～1.5; TiO 20.4～1.0; ZrO 21.0～1.7; ZnO 1.2～2.0.
In view of the difference of other pigment performances beyond selenium, cadmium dye and the selenium cadmium class, we have developed its optimal prescription respectively.The desirable compositing range that is 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.
The preferred version compositing range that is suitable for selenium-cadmium dye other colour on glazed ceramics in addition 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.
Each component in above-mentioned each 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.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 You point 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 Zhuan decorations of various ceramic blank You, " burst porcelain " phenomenon can not occur.
4, chemical stability is good.
(1) Zai 4% acetum Zhong under 22 ± 2 ℃ of temperature of Yu, soaked 24 hours, and the Yong atomic absorption spectrophotometer is measured the stripping quantity PPM Zhi of acetic acid soak Zhong lead, Ge, Pb=0.05～0.30mg/dm2，Cd＝0.03～0.08mg/dm 2。
(2) the acetum Zhong of Zai 4% under 22 ± 2 ℃ of temperature of Yu, soaked 24 hours, and Yong water is cleaned airing, and it is unchanged to observe color harmony gloss.
(3) Na of Zai 0.5%2CO 3Solution Zhong soaked 32 hours under 60 ± 2 ℃ of temperature of Yu, and Yong water is cleaned airing, and 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 Zhuan decorations of the multiple ceramics such as hard-paste, soft-paste, Shi porcelain, fine earthenware, bone china and vitreous ceramic. Simultaneously, the Zhuan decorations that also can be used for enamelware.

Claims (10)

1, this series pigments 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; 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% by SnO 2With from ZrO 2, TiO 2, stablizer three parts formed of the component that chooses among the ZnO form.
2, according to claim 1, the compositing range that it is characterized in that described main body flux is (mol%): PbO 10.0～26.0; B 2O 33.5～15.0; SiO 248.0～60.0; Al 2O 33.0～7.0.
3, according to claim 1, (mol%): the Li that it is characterized in that the compositing range of described composite fluxing agent is 2O 1.5～4.2; Na 2O 1.5～5.9; K 2O 0.5～1.0; MgO 0.5～5.0.
4, according to claim 1, (mol%): the SnO that it is characterized in that the compositing range of described stablizer is 20.2～1.8; TiO 20.4～1.0; ZrO 21.0～1.7; ZnO 1.2～2.0.
5, according to claim 1, it is characterized in that described flux, its desirable compositing range that is 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.
6, according to claim 1, it is characterized in that described flux, its preferred version compositing range that is suitable for other colour on glazed ceramics 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.
7, a kind of preparation method of low-temp ceramics over-glaze pigment is characterized in 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.
8,, it is characterized in that described wet grinding media is water or alcohol, preferably alcohol according to claim 7.
9, according to claim 7, it is characterized in that the preparation method of described toner is: ℃ following calcining of weigh batching → wet ball grinding mixing → oven dry → 600～1350 forms.
10, according to claim 7, it is characterized in that the preparation method of described flux is: weigh batching → dry mixed → 1250 ℃～1320 ℃ of following fusion → shrend → oven dry form.
CN 89106845 1989-10-25 1989-10-25 Low-temp. ceramic glazing dyestuff and its preparation method Expired - Lifetime CN1021112C (en)

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

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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

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CN1042698A true CN1042698A (en) 1990-06-06
CN1021112C CN1021112C (en) 1993-06-09

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Cited By (9)

* Cited by examiner, † Cited by third party
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
CN102627478A (en) * 2012-04-28 2012-08-08 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
CN102731157A (en) * 2012-06-14 2012-10-17 卡罗比亚釉料（昆山）有限公司 Lead-containing assistant of frit used for preparation of ceramics
CN101314549B (en) * 2007-05-29 2012-12-12 卡塔罗尼安-阿拉贡斯矿业公司 Metallic glaze composition
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
CN116282924A (en) * 2023-03-28 2023-06-23 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

Cited By (9)

* Cited by examiner, † Cited by third party
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
CN101314549B (en) * 2007-05-29 2012-12-12 卡塔罗尼安-阿拉贡斯矿业公司 Metallic glaze composition
CN102627478A (en) * 2012-04-28 2012-08-08 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
CN102731157A (en) * 2012-06-14 2012-10-17 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
CN116282924A (en) * 2023-03-28 2023-06-23 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

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Owner name: ZIBO FULU NEW MATERIAL CO., LTD.

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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.

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Granted publication date: 19930609