CN103086749B - In-situ synthesis method of zirconium silicate encapsulated carbon black pigment by microwave heating - Google Patents
In-situ synthesis method of zirconium silicate encapsulated carbon black pigment by microwave heating Download PDFInfo
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- CN103086749B CN103086749B CN201310072693.0A CN201310072693A CN103086749B CN 103086749 B CN103086749 B CN 103086749B CN 201310072693 A CN201310072693 A CN 201310072693A CN 103086749 B CN103086749 B CN 103086749B
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Abstract
The invention discloses an in-situ synthesis method of zirconium silicate encapsulated carbon black pigment by microwave heating. According to the method, powdered thermosetting phenol resin is adopted as a raw material to synthesize a black pigment with high encapsulation rate at a temperature of between 900 and 1,000 DEG C by utilizing a non-hydrolytic sol-gel in-situ synthesis technology. The synthesis method is simple in process, high in synthesis speed and low in synthesis temperature; and the prepared black pigment has a pure color and stable performance, is high in using temperature reaching 1,300 DEG C, can be widely applied to high-temperature glaze of various ceramic products, and has high economic value.
Description
Technical field
The invention belongs to ceramic (pottery) field, be specifically related to a kind of method of microwave heating original position synthetic silicic acid zirconium parcel carbon black colorant.
Background technology
In the black pigment using in Production of Ceramics at present, remove (Cr, Fe)
2o
3outside corundum type, other is spinel type colorant, as FeOFe
2o
3, Co-Cr-Fe, Co-Mn-Fe, Co-Mn-Cr-Fe, Co-Ni-Cr-Fe, Co-Mn-Ni-Cr-Fe, Co-Mn-Al-Cr-Fe, Co-Ni-Cr-Fe-Si etc.Although spinel type colorant Stability Analysis of Structures, have high temperature resistant, to atmosphere susceptibility little with the good feature of chemical stability, these colorants only in lime glaze colour generation best, and require in lime glaze without zinc, without magnesium, or low zinc, low magnesium.These colorants are unsettled in calcium magnesium glaze, are in most cases to form more stable spinel, make it to become grey or greyish-green; Although and stable in calcium zinc glaze, be off color, black middle band reddish-brown, and easily make glaze bubble.And black pigment FeOFe
2o
3easily be subject to the impact of atmosphere.Although manganese is conducive to black pigment colour generation, it tends to cause produce in glaze bubble.Cobalt is the distinct indispensable composition of black pigment, if but synthetic bad meeting is that colorant is general green or general red, and to prepare bright-coloured black pigment, the consumption of its cobalt oxide is more, and the price of cobalt oxide, a kind of black using in architectural pottery is produced oozes fancy glaze, and the composition of its colour generation is ruthenium salt, ruthenium is a kind of precious metal, and its price is tens times of gold., all there is certain deficiency in the existing technology of preparing of these black pigments in sum.Be subject to the impact of atmosphere (as FeOFe
2o
3) be subject to the impact of composition of glaze or price costliness very etc.
The stability of colorant is a difficult problem, especially high temperature (1300 ℃) colorant in Production of Ceramics always, only having at present cadmium-selenium red (Huang) colorant of zirconium silicate parcel is the colorant of high-temperature stable, and the Application and Development of the occlusion pigment of other colors there is not yet report.Therefore, developing the black occlusion pigment that can stablize color development under a kind of high temperature has great importance.
Summary of the invention
The technical problem to be solved in the present invention is to provide the method for the microwave heating original position synthetic silicic acid zirconium parcel carbon black colorant that a kind of technique is simple, raw materials cost is lower, synthetic ratio is high, use temperature is high.
For solving above technical problem, technical scheme of the present invention is: a kind of method of microwave heating original position synthetic silicic acid zirconium parcel carbon black colorant, in turn includes the following steps:
1. by the anhydrous ZrCl of technical pure
4join technical pure Si (OC
2h
5)
4in solution, control Zr
+ 4with Si
+ 4mol ratio is 1:1.2, and at room temperature high-speed stirring forms gel mixture A after 20 minutes;
2. powdered thermosetting resol, LiF are joined in dehydrated alcohol, the consumption of controlling powdered thermosetting resol is ZrCl
45 ~ 8% of weight, the concentration in dehydrated alcohol is 10%; Li
+ 1with Zr
+ 4mol ratio be 1:0.35, liquid B is uniformly mixed after stirring;
3. A mutually mixed and stirred with B, being then placed in 110 ℃ of oil bath pan reflux and obtaining precursor sol, then precursor sol being placed in to baking oven dry, obtaining xerogel;
4. xerogel is packed in crucible and adopt the method synthesizing black colorant of adding a cover microwave heating, synthesis technique control is: room temperature ~ 650 ℃, and the heating-up time is 5 minutes, is incubated 30 minutes; 650 ℃ ~ synthesis temperature, the heating-up time is 10 minutes, is incubated 10 minutes; Then naturally cooling.
Described synthesis temperature is 900 ~ 1000 ℃.
Above-mentioned black pigment encapsulation ratio >=45%, mean particle size≤8 μ m, use temperature are 1300 ℃.
Innovation of the present invention is to adopt brand-new non-hydrolytic sol-gel in situ synthetic technology to synthesize the black pigment that encapsulation ratio is high at 900 ~ 1000 ℃ of temperature, and this black pigment has been compared following characteristics with existing black pigment:
1, occlusion pigment colour generation is pure stable, can not be subject to the impact of the factors such as composition, firing atmosphere of glaze;
2, occlusion pigment use temperature reaches 1300 ℃;
3, the preparation technology of occlusion pigment is simple, resultant velocity is fast, encapsulation ratio is high, cost is low.
Embodiment
By embodiment, the present invention is further detailed explanation below.
Embodiment mono-:
The technical process that zirconium silicate parcel carbon black is prepared black pigment is:
The first step: by the anhydrous ZrCl of technical pure
4join technical pure Si (OC
2h
5)
4in solution, control Zr
+ 4with Si
+ 4mol ratio is 1:1.2, and at room temperature high-speed stirring forms gel mixture A after 20 minutes;
Second step: powdered thermosetting resol, LiF are joined in dehydrated alcohol, and the consumption of controlling powdered thermosetting resol is ZrCl
48% of weight, the concentration in dehydrated alcohol is 10%; Li
+ 1with Zr
+ 4mol ratio be 1:0.35, liquid B is uniformly mixed after stirring;
The 3rd step: A mutually mixed and stirred with B, be then placed in 110 ℃ of oil bath pan reflux and obtain precursor sol, then precursor sol being placed in to baking oven dry, obtaining xerogel;
The 4th step: xerogel is packed in crucible and adopts the method synthesizing black colorant of adding a cover microwave heating, and synthesis technique control is: room temperature ~ 650 ℃, the heating-up time is 5 minutes, is incubated 35 minutes; 650 ~ 1000 ℃, the heating-up time is 10 minutes, is incubated 10 minutes; Then naturally cooling, whole heat-processed does not need sealing and atmosphere protection.
Embodiment bis-:
The technical process that zirconium silicate parcel carbon black is prepared black pigment is:
The first step: by the anhydrous ZrCl of technical pure
4join technical pure Si (OC
2h
5)
4in solution, control Zr
+ 4with Si
+ 4mol ratio is 1:1.2, and at room temperature high-speed stirring forms gel mixture A after 20 minutes;
Second step: powdered thermosetting resol, LiF are joined in dehydrated alcohol, and the consumption of controlling powdered thermosetting resol is ZrCl
46% of weight, the concentration in dehydrated alcohol is 10%; Li
+ 1with Zr
+ 4mol ratio be 1:0.35, liquid B is uniformly mixed after stirring;
The 3rd step: A mutually mixed and stirred with B, be then placed in 110 ℃ of oil bath pan reflux and obtain precursor sol, then precursor sol being placed in to baking oven dry, obtaining xerogel;
The 4th step: xerogel is packed in crucible and adopts the method synthesizing black colorant of adding a cover microwave heating, and synthesis technique control is: room temperature ~ 650 ℃, the heating-up time is 5 minutes, is incubated 35 minutes; 650 ~ 950 ℃, the heating-up time is 10 minutes, is incubated 10 minutes; Then naturally cooling, whole heat-processed does not need sealing and atmosphere protection.
Embodiment tri-:
The technical process that zirconium silicate parcel carbon black is prepared black pigment is:
The first step: by the anhydrous ZrCl of technical pure
4join technical pure Si (OC
2h
5)
4in solution, control Zr
+ 4with Si
+ 4mol ratio is 1:1.2, and at room temperature high-speed stirring forms gel mixture A after 20 minutes;
Second step: powdered thermosetting resol, LiF are joined in dehydrated alcohol, and the consumption of controlling powdered thermosetting resol is ZrCl
45% of weight, the concentration in dehydrated alcohol is 10%; Li
+ 1with Zr
+ 4mol ratio be 1:0.35, liquid B is uniformly mixed after stirring;
The 3rd step: A mutually mixed and stirred with B, be then placed in 110 ℃ of oil bath pan reflux and obtain precursor sol, then precursor sol being placed in to baking oven dry, obtaining xerogel;
The 4th step: xerogel is packed in crucible and adopts the method synthesizing black colorant of adding a cover microwave heating, and synthesis technique control is: room temperature ~ 650 ℃, the heating-up time is 5 minutes, is incubated 35 minutes; 650 ~ 900 ℃, the heating-up time is 10 minutes, is incubated 10 minutes; Then naturally cooling, whole heat-processed does not need sealing and atmosphere protection.
It is as follows that the encapsulation ratio of the obtained black pigment of above-described embodiment 1-3 and average granularity carry out characterization result:
Listed is above only zirconium silicate parcel black pigment preparation method's of the present invention preferred embodiment, certainly can not limit with this interest field of the present invention, therefore the equivalent variations of doing according to the present patent application the scope of the claims, still belongs to the scope that the present invention is contained.
Claims (1)
1. a method for microwave heating original position synthetic silicic acid zirconium parcel carbon black colorant, in turn includes the following steps:
1. by the anhydrous ZrCl of technical pure
4join technical pure Si (OC
2h
5)
4in solution, control Zr
+ 4with Si
+ 4mol ratio is 1:1.2, and at room temperature high-speed stirring forms gel mixture A after 20 minutes;
2. powdered thermosetting resol, LiF are joined in dehydrated alcohol, the consumption of controlling powdered thermosetting resol is ZrCl
45 ~ 8% of weight, the concentration in dehydrated alcohol is 10%; Li
+ 1with Zr
+ 4mol ratio be 1:0.35, liquid B is uniformly mixed after stirring;
3. A mutually mixed and stirred with B, being then placed in 110 ℃ of oil bath pan reflux and obtaining precursor sol, then precursor sol being placed in to baking oven dry, obtaining xerogel;
4. xerogel is packed in crucible and adopt the method synthesizing black colorant of adding a cover microwave heating, synthesis technique control is: room temperature ~ 650 ℃, and the heating-up time is 5 minutes, is incubated 30 minutes; 650 ℃ ~ synthesis temperature, the heating-up time is 10 minutes, is incubated 10 minutes; Then naturally cooling;
Described synthesis temperature is 900 ~ 1000 ℃;
Described black pigment encapsulation ratio >=45%, mean particle size≤8 μ m, use temperature are 1300 ℃.
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| CN201310072693.0A CN103086749B (en) | 2013-03-07 | 2013-03-07 | In-situ synthesis method of zirconium silicate encapsulated carbon black pigment by microwave heating |
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| CN103086749B true CN103086749B (en) | 2014-04-16 |
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Families Citing this family (3)
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| CN103435766B (en) * | 2013-08-30 | 2015-06-24 | 西北工业大学 | Boron-zirconium-silicon ternary modified phenolic resin and preparation method thereof |
| CN107312360A (en) * | 2017-06-24 | 2017-11-03 | 姚文澄 | A kind of zirconium silicate wraps up the preparation method of black material |
| CN107936618A (en) * | 2017-11-25 | 2018-04-20 | 景德镇陶瓷大学 | A kind of fused salt auxiliary prepares the method for zirconium silicate parcel carbon black colorant and its obtained product |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102241529A (en) * | 2011-05-20 | 2011-11-16 | 景德镇陶瓷学院 | Preparation method of ceramic pigment wrapping carbon black |
| CN102433033A (en) * | 2011-09-02 | 2012-05-02 | 景德镇陶瓷学院 | Method for preparing carbon black inclusion pigment in situ by nonhydrolytic sol-gel process |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102241529A (en) * | 2011-05-20 | 2011-11-16 | 景德镇陶瓷学院 | Preparation method of ceramic pigment wrapping carbon black |
| CN102433033A (en) * | 2011-09-02 | 2012-05-02 | 景德镇陶瓷学院 | Method for preparing carbon black inclusion pigment in situ by nonhydrolytic sol-gel process |
Non-Patent Citations (2)
| Title |
|---|
| 彭静等.棕色尖晶石色料的微波合成与呈色性能研究.《硅酸盐通报》.2011,第30卷(第3期),719-723. |
| 棕色尖晶石色料的微波合成与呈色性能研究;彭静等;《硅酸盐通报》;20110630;第30卷(第3期);719-723 * |
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