CN101117452A - Method for preparing ultra-fine cobalt blue pigment under low-temperature - Google Patents
Method for preparing ultra-fine cobalt blue pigment under low-temperature Download PDFInfo
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- CN101117452A CN101117452A CNA2007100183642A CN200710018364A CN101117452A CN 101117452 A CN101117452 A CN 101117452A CN A2007100183642 A CNA2007100183642 A CN A2007100183642A CN 200710018364 A CN200710018364 A CN 200710018364A CN 101117452 A CN101117452 A CN 101117452A
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Abstract
A method for preparing superfine cobalt blue colorant at low temperature comprises the following steps: firstly, cobaltosic oxide, aluminium hydroxide, zinc oxide and chromic oxide are mixed according to the general chemical formula of Co1-xZnxAl2-yCryO4 to obtain reactants, wherein x is more than or equal to 0 and is less than 1, while y is more than or equal to 0 and is less than or equal to 2; secondly, one sort or more sorts of KOH, NaOH, KCl, NaCl, Li2SO4 and Na2SO4 are added into the reactants to obtain mixture after being mixed uniformly; finally, the mixture is calcined 1 to 2 hours at the temperature ranging from 800 DEG C to 1,000 DEG C and then the calcined products is under the treatments of grinding, cleaning and filtration. The invention possesses simple technical process and equipment, convenient operation, cheap and easily obtained raw material and low cost for preparing colorant; moreover, the colorant obtained through adopting the preparing method is characterized in high development degree of crystal grain, ideal chromophoric effect of colorant, fine granularity, less agglomeration and good homogeneity etc.; meanwhile, the introduction of salt can lower synthesis temperature.
Description
Technical field
The invention belongs to material science, be specifically related to a kind of method of preparing ultra-fine cobalt blue pigment under low-temperature.
Background technology
Cobalt blue is the important blue colorant of spinel type, also can be described as the aluminic acid cobalt blue.Simplest formula is CoAl
2O
4, positively charged ion wherein can be replaced by other metal ion, thereby prepares the colorant of the different depths or different tones.Compare with other blue colorant, have excellent photostabilization, weathering resistance, thermotolerance, chemical resistance, performance such as nontoxic, therefore be widely used in high-temperature resistant coating, pottery, enamel, glass, coloring plastic.At present, the method for preparing this colorant mainly contains conventional solid-state method and some wet chemical methods.Adopt traditional technology synthetic pigment because synthesis temperature is higher, generally need more than 1200 ℃, granularity is thick and thereby skewness influences its result of use, often need further ball milling to use, energy consumption is higher, and often influences the purity of pigment because of sneaking into some impurity during ball milling.
The wet chemical method of synthetic this colorant comprises hydrothermal method, the precipitator method and microemulsion method etc.Though the granularity of the synthetic colorant of these methods is thinner, it is comparatively serious to reunite, and the crystalline state of colorant is relatively poor, and color development, the erosion resistance of colorant seriously reduce.These methods need some expensive raw materials in addition, and technology is complicated higher to equipment requirements, is unfavorable for suitability for industrialized production.The Yang Guiqin of University Of Tianjin with rose vitriol and Tai-Ace S 150, chromium chloride and titanium tetrachloride by certain amount of substance than mixing and water adding stirring and dissolving, heat up then, adding sodium hydroxide solution to pH value is 8～10, stirring reaction, ageing, water washing and precipitating thing, the throw out slurry is cultivated 160～260 ℃ of following hydro-thermals, again the liquid phase hydro-thermal is cultivated material through filtration, dry, pulverizing, carry out solid phase high temperature crystallization at 900 ℃～1200 ℃ and make the nanometer cobalt blue colorant.Though this method can obtain nano level zaffre, technology is quite complicated, and the crystallization temperature height.
Summary of the invention
The object of the present invention is to provide a kind of preparation technology simple, synthesis temperature is low, and is low for equipment requirements, the method of the preparing ultra-fine cobalt blue pigment under low-temperature that energy consumption is low, the zaffre that obtains with this method has fine size, and the crystal grain crystalline state is good, the characteristics that the colorant color development is good.
For achieving the above object, the technical solution used in the present invention is: 1) at first, tricobalt tetroxide, aluminium hydroxide, zinc oxide and chromic oxide are pressed chemical general formula Co
1-xZn
xAl
2-yCr
yO
4Carry out proportioning and obtain reactant, wherein 0≤x＜1,0≤y≤2; Secondly, KOH, the NaOH, KCl, NaCl, the Li that in reactant, add reactant quality 80%-200%
2SO
4, Na
2SO
4In one or more mix and obtain mixture; At last, mixture was calcined 1-2 hour in 800 ℃-1000 ℃, with the calcinate porphyrize, cleaned, filtration can obtain lightness 29≤L*≤33, tone-2.5≤a*≤-5, the ultra-fine zaffre of-3.5≤b*≤-9.
It is good that the colorant that adopts preparation method of the present invention to obtain has a crystal grain development degree, the colorant color development is good, fine size, and it is light to reunite, characteristics such as homogeneity is good, simultaneously, the introducing of salt can reduce synthesis temperature, and technical process of the present invention and equipment are simple, easy to operate, raw material cheaply is easy to get, and the colorant preparation cost is low.
Description of drawings
Fig. 1 is the XRD figure of the embodiment of the invention 1 colorant, and wherein X-coordinate is a diffraction angle, and ordinate zou is a diffracted intensity.
Fig. 2 is the SEM figure of the embodiment of the invention 1 colorant sample.
Embodiment
Below in conjunction with drawings and Examples the present invention is described in further detail.
Embodiment 1: at first, tricobalt tetroxide and chromic oxide are pressed chemical general formula Co
1Cr
2O
4Carry out proportioning and obtain reactant, secondly, the KOH of adding reactant quality 100% and NaOH mix and obtain mixture in reactant; At last, mixture was calcined 1 hour in 900 ℃, with the calcinate porphyrize, cleaned, filtration gets final product.As seen from Figure 1, the principal crystalline phase of gained colorant is the spinel type Leyden blue, does not have other dephasign and exists; As seen from Figure 2, the combination colour material granularity is less, and it is less to distribute, between 200～400nm.Crystal grain is grown better, and it is lighter to reunite.
Embodiment 2: at first, tricobalt tetroxide, aluminium hydroxide, zinc oxide and chromic oxide are pressed chemical general formula Co
0.5Zn
0.5Al
1Cr
1O
4Carry out proportioning and obtain reactant, secondly, the NaOH of adding reactant quality 150% and KOH mix and obtain mixture in reactant; At last, mixture was calcined 2 hours in 800 ℃, with the calcinate porphyrize, cleaned, filtration gets final product.
Embodiment 3: at first, tricobalt tetroxide, aluminium hydroxide and zinc oxide are pressed chemical general formula Co
0.2Zn
0.8Al
2O
4Carry out proportioning and obtain reactant, secondly, the KCl that adds reactant quality 80% in reactant mixes and obtains mixture; At last, mixture was calcined 1.6 hours in 1000 ℃, with the calcinate porphyrize, cleaned, filtration gets final product.
Embodiment 4: at first, tricobalt tetroxide, aluminium hydroxide, zinc oxide and chromic oxide are pressed chemical general formula Co
0.7Zn
0.3Al
0.5Cr
1.5O
4Carry out proportioning and obtain reactant, secondly, in reactant, add the Li of reactant quality 180%
2SO
4And Na
2SO
4Mix and obtain mixture; At last, mixture was calcined 4 hours in 850 ℃, with the calcinate porphyrize, cleaned, filtration gets final product.
Embodiment 5: at first, tricobalt tetroxide, aluminium hydroxide, zinc oxide and chromic oxide are pressed chemical general formula Co
0.9Zn
0.1Al
1.4Cr
0.6O
xCarry out proportioning and obtain reactant, secondly, in reactant, add the Li of reactant quality 120%
2SO
4And Na
2SO
4Mix and obtain mixture; At last, mixture was calcined 0.5 hour in 950 ℃, with the calcinate porphyrize, cleaned, filtration gets final product.
Embodiment 6: at first, tricobalt tetroxide, aluminium hydroxide, zinc oxide and chromic oxide are pressed chemical general formula Co
0.1Zn
0.9Al
1.8Cr
0.2O
4Carry out proportioning and obtain reactant, secondly, the KCl of adding reactant quality 200% and NaCl mix and obtain mixture in reactant; At last, mixture was calcined 1.1 hours in 930 ℃, with the calcinate porphyrize, cleaned, filtration gets final product.
Embodiment 7: at first, tricobalt tetroxide, aluminium hydroxide, zinc oxide and chromic oxide are pressed chemical general formula Co
0.6Zn
0.4Al
0.2Cr
1.8O
4Carry out proportioning and obtain reactant, secondly, the KCl of adding reactant quality 170% and NaCl mix and obtain mixture in reactant; At last, mixture was calcined 1.5 hours in 970 ℃, with the calcinate porphyrize, cleaned, filtration gets final product.
Claims (8)
1. the method for a preparing ultra-fine cobalt blue pigment under low-temperature is characterized in that:
1) at first, tricobalt tetroxide, aluminium hydroxide, zinc oxide and chromic oxide are pressed chemical general formula Co
1-xZn
xAl
2-yCr
yO
4Carry out proportioning and obtain reactant, wherein 0≤x＜1,0≤y≤2;
2) KOH, the NaOH, KCl, NaCl, the Li that secondly, in reactant, add reactant quality 80%-200%
2SO
4, Na
2SO
4In one or more mix and obtain mixture;
3) last, mixture was calcined 1-2 hour in 800 ℃-1000 ℃, with the calcinate porphyrize, to clean, filtration can obtain lightness 29≤L*≤33, tone-2.5≤a*≤-5, the ultra-fine zaffre of-3.5≤b*≤-9.
2. the method for preparing ultra-fine cobalt blue pigment under low-temperature according to claim 1 is characterized in that: at first, tricobalt tetroxide and chromic oxide are pressed chemical general formula Co
1Cr
2O
4Carry out proportioning and obtain reactant, secondly, the KOH of adding reactant quality 100% and NaOH mix and obtain mixture in reactant; At last, mixture was calcined 1 hour in 900 ℃, with the calcinate porphyrize, cleaned, filtration gets final product.As seen from Figure 1, the principal crystalline phase of gained colorant is the spinel type Leyden blue, does not have other dephasign and exists; As seen from Figure 2, the combination colour material granularity is less, and it is less to distribute, between 200～400nm.Crystal grain is grown better, and it is lighter to reunite.
3. the method for preparing ultra-fine cobalt blue pigment under low-temperature according to claim 1 is characterized in that: at first, tricobalt tetroxide, aluminium hydroxide, zinc oxide and chromic oxide are pressed chemical general formula Co
0.5Zn
0.5Al
1Cr
1O
4Carry out proportioning and obtain reactant, secondly, the NaOH of adding reactant quality 150% and KOH mix and obtain mixture in reactant; At last, mixture was calcined 2 hours in 800 ℃, with the calcinate porphyrize, cleaned, filtration gets final product.
4. the method for preparing ultra-fine cobalt blue pigment under low-temperature according to claim 1 is characterized in that: at first, tricobalt tetroxide, aluminium hydroxide and zinc oxide are pressed chemical general formula Co
0.2Zn
0.8Al
2O
4Carry out proportioning and obtain reactant, secondly, the KCl that adds reactant quality 80% in reactant mixes and obtains mixture; At last, mixture was calcined 1.6 hours in 1000 ℃, with the calcinate porphyrize, cleaned, filtration gets final product.
5. the method for preparing ultra-fine cobalt blue pigment under low-temperature according to claim 1 is characterized in that: at first, tricobalt tetroxide, aluminium hydroxide, zinc oxide and chromic oxide are pressed chemical general formula Co
0.7Zn
0.3Al
0.5Cr
1.5O
4Carry out proportioning and obtain reactant, secondly, in reactant, add the Li of reactant quality 180%
2SO
4And Na
2SO
4Mix and obtain mixture; At last, mixture was calcined 4 hours in 850 ℃, with the calcinate porphyrize, cleaned, filtration gets final product.
6. the method for preparing ultra-fine cobalt blue pigment under low-temperature according to claim 1 is characterized in that: at first, tricobalt tetroxide, aluminium hydroxide, zinc oxide and chromic oxide are pressed chemical general formula Co
0.9Zn
0.1Al
1.4Cr
0.6O
4Carry out proportioning and obtain reactant, secondly, in reactant, add the Li of reactant quality 120%
2SO
4And Na
2SO
4Mix and obtain mixture; At last, mixture was calcined 0.5 hour in 950 ℃, with the calcinate porphyrize, cleaned, filtration gets final product.
7. the method for preparing ultra-fine cobalt blue pigment under low-temperature according to claim 1 is characterized in that: at first, tricobalt tetroxide, aluminium hydroxide, zinc oxide and chromic oxide are pressed chemical general formula Co
0.1Zn
0.9Al
1.8Cr
0.2O
4Carry out proportioning and obtain reactant, secondly, the KCl of adding reactant quality 200% and NaCl mix and obtain mixture in reactant; At last, mixture was calcined 1.1 hours in 930 ℃, with the calcinate porphyrize, cleaned, filtration gets final product.
8. the method for preparing ultra-fine cobalt blue pigment under low-temperature according to claim 1 is characterized in that: at first, tricobalt tetroxide, aluminium hydroxide, zinc oxide and chromic oxide are pressed chemical general formula Co
0.6Zn
0.4Al
0.2Cr
1.8O
4Carry out proportioning and obtain reactant, secondly, the KCl of adding reactant quality 170% and NaCl mix and obtain mixture in reactant; At last, mixture was calcined 1.5 hours in 970 ℃, with the calcinate porphyrize, cleaned, filtration gets final product.
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| CN100569869C CN100569869C (en) | 2009-12-16 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030563A (en) * | 2010-10-20 | 2011-04-27 | 景德镇陶瓷学院 | Method for preparing cobalt blue material for decorating ceramic |
| CN102241528A (en) * | 2011-05-11 | 2011-11-16 | 景德镇陶瓷学院 | Process for preparing spherical nanometer spinel zaffre by hydrothermal method |
| CN103708849A (en) * | 2013-12-20 | 2014-04-09 | 佛山市三水区康立泰无机合成材料有限公司 | Color material for ceramic ink-jet printing and preparation method thereof |
| CN104403376A (en) * | 2014-12-18 | 2015-03-11 | 常熟市环虹化工颜料厂 | Preparation method of cobalt blue pigment |
| CN111218131A (en) * | 2019-12-12 | 2020-06-02 | 西北永新涂料有限公司 | Preparation method for preparing cobalt blue/clay mineral hybrid pigment by solid-phase method |
| CN112158890A (en) * | 2020-08-21 | 2021-01-01 | 佛山市华意陶瓷颜料有限公司 | Low-temperature peacock blue pigment and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7014701B2 (en) * | 2003-08-27 | 2006-03-21 | Ferro Corporation | Inorganic pigments |
| CN100455630C (en) * | 2006-04-24 | 2009-01-28 | 天津大学 | Method for preparing nanometer cobalt blue dye |
-
2007
- 2007-07-27 CN CNB2007100183642A patent/CN100569869C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102241528A (en) * | 2011-05-11 | 2011-11-16 | 景德镇陶瓷学院 | Process for preparing spherical nanometer spinel zaffre by hydrothermal method |
| CN102241528B (en) * | 2011-05-11 | 2013-07-10 | 景德镇陶瓷学院 | Process for preparing spherical nanometer spinel zaffre by hydrothermal method |
| CN103708849A (en) * | 2013-12-20 | 2014-04-09 | 佛山市三水区康立泰无机合成材料有限公司 | Color material for ceramic ink-jet printing and preparation method thereof |
| CN104403376A (en) * | 2014-12-18 | 2015-03-11 | 常熟市环虹化工颜料厂 | Preparation method of cobalt blue pigment |
| CN111218131A (en) * | 2019-12-12 | 2020-06-02 | 西北永新涂料有限公司 | Preparation method for preparing cobalt blue/clay mineral hybrid pigment by solid-phase method |
| CN111218131B (en) * | 2019-12-12 | 2021-08-03 | 西北永新涂料有限公司 | Preparation method for preparing cobalt blue/clay mineral hybrid pigment by solid-phase method |
| CN112158890A (en) * | 2020-08-21 | 2021-01-01 | 佛山市华意陶瓷颜料有限公司 | Low-temperature peacock blue pigment and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN100569869C (en) | 2009-12-16 |
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