CN1831047A - Method for preparing nanometer cobalt blue dye - Google Patents
Method for preparing nanometer cobalt blue dye Download PDFInfo
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- CN1831047A CN1831047A CN 200610013525 CN200610013525A CN1831047A CN 1831047 A CN1831047 A CN 1831047A CN 200610013525 CN200610013525 CN 200610013525 CN 200610013525 A CN200610013525 A CN 200610013525A CN 1831047 A CN1831047 A CN 1831047A
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Abstract
This invention discloses a preparation method of nm cobalt blue, and it belongs to synthetic technique of nm spinel style colorant. This method includes following procedures cobaltous sulfate and aluminium sulphate, chromic chloride and titanium tetrachloride are mixed with water and agitated to solve, there mol ratio is that 1:(0.5-2): (0-3): (0-3), then they are heated and sodium hydrate solution is added to adjust pH value to 8-10. They are agitated, aging and water flushed, the precipitate stuff is hydrothermal cultivated at 160-260 degrees centigrade, then the hydrothermal cultivated stuff is filtrated, dried and crashed, finally it is solid phase high temperature crystallized at 900-1200 deg.C to get nm cobalt blue product. The advantage of this invention is that two step ways synthetic technique are used, so the particles can reach nm grade after high temperature crystallization, the particle diameter of cobalt blue particles made is small, the average particle diameter is 30-80nm, and its production technique is simple, energy consumption is relatively low.
Description
Technical field
The present invention relates to a kind of preparation method of nanometer cobalt blue, belong to the synthetic technology of nanometer spinel type pigment.
Background technology
Cobalt blue is important spinel type colored organic pigments, is the composite oxides with spinel structure.In a broad sense, spinelle type composite oxides is to be+8 by the summation of its each cationic positive oxidation value of forming in its simplest formula, and the based composite oxide that negative oxidation value-8 is provided by 4-2 oxygen.Can be represented by the formula as the simplest cobalt blue of chemical formula: CoAl
2O
4, also can be described as the aluminic acid cobalt blue.During practical application, positively charged ion wherein can replace by positively charged ions not of the same race by some, different numbers, thereby can prepare the mixed phase pigment of the different depths or different tones.
Cobalt blue dye is compared with other blue pigments, and its distinguishing feature is to have good heat endurance, photostabilization, weathering resistance and chemical-resistant, is widely used in fields such as painted and art painting such as high-temperature resistant coating, plastics, pottery, enamel, glass.Especially in requiring super weather resistance (particularly super tint retention, gloss retention and resistance to chalking) system, then more to use this pigment.Though but common cobalt blue dye has the patience of good heat endurance, photostabilization, weathering resistance and chemical-resistant, but because its size-grade distribution is wide, particle more greatly and harder, so do not have pigment performance preferably, the kind of this class pigment is few at present, and quality is also suddenly waited to improve.Nanometer cobalt blue has better performance, and this high-grade pigment can be used for the painted of super permanent seal cooling coating and engineering plastics; Also have some special purpose in addition, the automobile lamp that for example is applied to require high transmission rate is with in the coating, is applied to the painted etc. of fluor in the colour television set CRT teletron.Therefore some famous companies in the world, sheoherd color company, Harshaw Chemical company as the U.S., Beyer Co., Ltd, BASF AG of Germany, the company etc. that refines big day of the Blythe Colours company of Britain and Japan all produces the very high mineral dye of this value added.
China does not still have high-grade nanometer cobalt blue product.The import of still needing of high-grade nanometer cobalt blue, but because its synthesis technique complexity, therefore the energy consumption height costs an arm and a leg, and has limited use.
The preparation method that cobalt blue is traditional adopts dry method mostly, i.e. the preparation method of direct solid phase high-temperature calcination behind the raw material blending.Its shortcoming is an incinerating temperature height, the energy consumption height, and the pigment particle size that makes is big, and size-grade distribution is inhomogeneous, is a bit darkish in color.Existing method is different with traditional method, is earlier reactant to be made precursor through liquid-phase precipitation, again through the preparation process (wet method) of high-temperature calcination, though increase with the made pigment performance of wet method, color is comparatively distinct, but particle diameter still has the hundreds of nanometer, does not reach the service requirements of expensive goods.For reducing particle diameter, can further adopt the method for high-energy ball milling, but energy consumption is higher, also may introduce impurity, and carry out ball milling to heavens, also might generating unit divide the mechanics chemical reaction.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of nanometer cobalt blue, this method has the advantages that technology is simple, energy consumption is lower.
The present invention is realized by following technical proposals.A kind of preparation method of nanometer cobalt blue is characterized in that may further comprise the steps:
1. be 1 with rose vitriol and Tai-Ace S 150, chromium chloride and titanium tetrachloride by the ratio of amount of substance: (0.5～2): (0～3): (0～0.3) mixing and water adding stirring and dissolving, the aqueous solution are warming up to 40～80 ℃, add 3molL
-1NaOH solution to regulate pH value of water solution be 8～10, stirring reaction, ageing 1～4 hour will precipitate with clear liquid and separate, and the water washing and precipitating thing, make the throw out slurry;
2. the throw out slurry that step 1 is made was cultivated 1～8 hour 160～260 ℃ of following hydro-thermals, made the liquid phase hydro-thermal and cultivated material;
3. the liquid phase hydro-thermal that step 2 made cultivate material through filtration under diminished pressure, 80～100 ℃ of dryings, put into the mortar porphyrize, carried out solid phase high temperature crystallization 1～8 hour at 900～1200 ℃, obtain the nanometer cobalt blue product.
The invention has the advantages that: owing to adopt the two-step approach synthetic technology of cultivation of liquid phase hydro-thermal and solid phase high temperature crystallization, with particle after the crystallization that reaches a high temperature is nano level purpose, obtained cobalt green pigment particle size is little, median size is 30～80nm, and production technique is simpler, energy consumption is relatively low, the product purity height.。
Description of drawings
Fig. 1 is the TEM photo of the embodiment of the invention 1 made nanometer cobalt blue.
Embodiment
Embodiment 1:
Take by weighing 84.3 gram rose vitriols and 199.8 gram Tai-Ace S 150, add the water stirring and dissolving, when being warming up to 80 ℃, add 3molL
-1NaOH solution to pH value be 9, ageing 2 hours will precipitate and clear liquid separates, and water washing and precipitating thing is cultivated the throw out slurry 6 hours 220 ℃ of following hydro-thermals; To cultivate material filtration under diminished pressure, 80 ℃ dry down, put into the mortar porphyrize, 1000 ℃ of crystallization 4 hours, obtain product, productive rate 93%, median size is 50nm.
Embodiment 2:
Take by weighing 84.3 gram rose vitriols, 139.9 gram Tai-Ace S 150,127.7 gram chromium chlorides, 5.7 gram TiCl
4(amounting to from the density of its solution of purchase) adds the water stirring and dissolving, when being warming up to 80 ℃, adds 3molL
-1NaOH solution to pH value be 9, ageing 2 hours will precipitate and clear liquid separates, and water washing and precipitating thing is cultivated the throw out slurry 4 hours 240 ℃ of following hydro-thermals; To cultivate material filtration under diminished pressure, 80 ℃ dry down, put into the mortar porphyrize, 1100 ℃ of crystallization 4 hours, obtain product, productive rate 93%, median size is 50nm.
Embodiment 3:
Take by weighing 84.3 gram rose vitriols, 99.9 gram Tai-Ace S 150,199.5 gram chromium chlorides, 11.4 gram TiCl
4(amounting to from the density of its solution of purchase) adds the water stirring and dissolving, when being warming up to 80 ℃, adds 3molL
-1NaOH solution to pH value be 9, ageing 2 hours will precipitate and clear liquid separates, and water washing and precipitating thing is cultivated the throw out slurry 4 hours 240 ℃ of following hydro-thermals; To cultivate material filtration under diminished pressure, 80 ℃ dry down, put into the mortar porphyrize, 1100 ℃ of crystallization 4 hours, obtain product, productive rate 93%, median size is 50nm.
Claims (1)
1. the preparation method of a nanometer cobalt blue is characterized in that may further comprise the steps:
1). is 1 with rose vitriol and Tai-Ace S 150, chromium chloride and titanium tetrachloride by the ratio of amount of substance: (0.5～2): (0～3): (0～0.3) mixing and water adding stirring and dissolving, the aqueous solution are warming up to 40～80 ℃, add 3molL
-1NaOH solution to regulate pH value of water solution be 8～10, stirring reaction, ageing 1～4 hour will precipitate with clear liquid and separate, and the water washing and precipitating thing, make the throw out slurry;
2). the throw out slurry that step 1) makes was cultivated 1～8 hour 160～260 ℃ of following hydro-thermals, made the liquid phase hydro-thermal and cultivate material;
3). with step 2) the liquid phase hydro-thermal that makes cultivate material dry down through filtration under diminished pressure, 80～100 ℃, put into the mortar porphyrize, carried out solid phase high temperature crystallization 1～8 hour at 900～1200 ℃, obtain the nanometer cobalt blue product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100135254A CN100455630C (en) | 2006-04-24 | 2006-04-24 | Method for preparing nanometer cobalt blue dye |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100135254A CN100455630C (en) | 2006-04-24 | 2006-04-24 | Method for preparing nanometer cobalt blue dye |
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| CN1831047A true CN1831047A (en) | 2006-09-13 |
| CN100455630C CN100455630C (en) | 2009-01-28 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100569869C (en) * | 2007-07-27 | 2009-12-16 | 陕西科技大学 | A kind of method of preparing ultra-fine cobalt blue pigment under low-temperature |
| CN102030563A (en) * | 2010-10-20 | 2011-04-27 | 景德镇陶瓷学院 | Method for preparing cobalt blue material for decorating ceramic |
| CN104910673A (en) * | 2015-05-25 | 2015-09-16 | 陕西理工学院 | Preparation method of green pigment capable of reflecting infrared ray, and thermal-insulation paint |
| CN106379907A (en) * | 2016-08-12 | 2017-02-08 | 陕西科技大学 | Preparation method for purple archaistic ceramic pigment |
| CN106629867A (en) * | 2016-12-21 | 2017-05-10 | 中国科学院兰州化学物理研究所 | Method for preparing light-blue cobalt blue hybrid pigment from aluminum-rich non-metallic minerals |
| CN106809885A (en) * | 2017-01-10 | 2017-06-09 | 上海印钞有限公司 | A kind of preparation method of nanometer cobalt blue dye |
| CN107777727A (en) * | 2017-11-06 | 2018-03-09 | 北京科技大学 | A kind of preparation method of Ba Al Mn O blue inorganic pigments |
| CN109181369A (en) * | 2018-10-15 | 2019-01-11 | 中国科学院兰州化学物理研究所 | Microwave hydrothermal auxiliary prepares high chroma cobalt blue/clay mineral hybrid pigment method |
| CN112441623A (en) * | 2020-11-17 | 2021-03-05 | 浙大宁波理工学院 | Preparation of high near-infrared reflection color pigment by using modified cobalt blue pigment |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2681837B2 (en) * | 1990-06-22 | 1997-11-26 | 大日精化工業株式会社 | Method for producing fine particle composite oxide blue green pigment |
| JP2599638B2 (en) * | 1990-06-22 | 1997-04-09 | 大日精化工業株式会社 | Fine-particle composite oxide blue-green pigment and method for producing the same |
| CN100439254C (en) * | 2004-11-12 | 2008-12-03 | 南京大学 | Preparation for nanometer cobalt compound |
-
2006
- 2006-04-24 CN CNB2006100135254A patent/CN100455630C/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100569869C (en) * | 2007-07-27 | 2009-12-16 | 陕西科技大学 | A kind of method of preparing ultra-fine cobalt blue pigment under low-temperature |
| CN102030563A (en) * | 2010-10-20 | 2011-04-27 | 景德镇陶瓷学院 | Method for preparing cobalt blue material for decorating ceramic |
| CN102030563B (en) * | 2010-10-20 | 2012-11-21 | 景德镇陶瓷学院 | Method for preparing cobalt blue material for decorating ceramic |
| CN104910673A (en) * | 2015-05-25 | 2015-09-16 | 陕西理工学院 | Preparation method of green pigment capable of reflecting infrared ray, and thermal-insulation paint |
| CN106379907B (en) * | 2016-08-12 | 2018-04-03 | 陕西科技大学 | A kind of preparation method of ceramic violet pigment modelled after an antique |
| CN106379907A (en) * | 2016-08-12 | 2017-02-08 | 陕西科技大学 | Preparation method for purple archaistic ceramic pigment |
| CN106629867B (en) * | 2016-12-21 | 2018-08-14 | 中国科学院兰州化学物理研究所 | The method for preparing high sapphirine cobalt blue hybrid pigment using rich aluminium nonmetallic mineral |
| CN106629867A (en) * | 2016-12-21 | 2017-05-10 | 中国科学院兰州化学物理研究所 | Method for preparing light-blue cobalt blue hybrid pigment from aluminum-rich non-metallic minerals |
| CN106809885A (en) * | 2017-01-10 | 2017-06-09 | 上海印钞有限公司 | A kind of preparation method of nanometer cobalt blue dye |
| CN106809885B (en) * | 2017-01-10 | 2019-07-12 | 上海印钞有限公司 | A kind of preparation method of nanometer cobalt blue dye |
| CN107777727A (en) * | 2017-11-06 | 2018-03-09 | 北京科技大学 | A kind of preparation method of Ba Al Mn O blue inorganic pigments |
| CN107777727B (en) * | 2017-11-06 | 2019-08-06 | 北京科技大学 | A kind of preparation method of Ba-Al-Mn-O blue inorganic pigment |
| CN109181369A (en) * | 2018-10-15 | 2019-01-11 | 中国科学院兰州化学物理研究所 | Microwave hydrothermal auxiliary prepares high chroma cobalt blue/clay mineral hybrid pigment method |
| CN112441623A (en) * | 2020-11-17 | 2021-03-05 | 浙大宁波理工学院 | Preparation of high near-infrared reflection color pigment by using modified cobalt blue pigment |
| CN112441623B (en) * | 2020-11-17 | 2022-06-14 | 浙大宁波理工学院 | Preparation of high near-infrared reflection color pigment by using modified cobalt blue pigment |
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| Publication number | Publication date |
|---|---|
| CN100455630C (en) | 2009-01-28 |
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Granted publication date: 20090128 Termination date: 20110424 |