CN102212365A - Preparation method for europium-doping calcium titanate fluorescent powder - Google Patents
Preparation method for europium-doping calcium titanate fluorescent powder Download PDFInfo
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- CN102212365A CN102212365A CN 201110091323 CN201110091323A CN102212365A CN 102212365 A CN102212365 A CN 102212365A CN 201110091323 CN201110091323 CN 201110091323 CN 201110091323 A CN201110091323 A CN 201110091323A CN 102212365 A CN102212365 A CN 102212365A
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Abstract
The invention relates to a preparation method for europium-doping calcium titanate fluorescent powder. The preparation method comprises the following steps of: (1) adding an aqueous ammonia solution into a tetra-n-butyl titanate solution at the room temperature so as to obtain a white precipitant, and washing the white precipitant so as to obtain a precursor; (2) dispersing the precursor in a mixing solution of ethylene glycol and ethylene dimine, and then stirring continuously so as to form a precursor suspending liquid; (3) respectively dissolving calcium acetate, europium nitrate and sodium hydroxide in deionized water, dropping into the precursor suspending liquid, adding polyethylene glycol 200, pouring into an agitated reactor after stirring and heating to 180-220 DEG C and reacting for 8-12h; and (4) after reaction, cooling to the room temperature, washing and drying a product so as to obtain the fluorescent powder. The preparation method has the advantages that the preparation method is simple, the cost is low, required production equipment is simple, the reaction temperature is low, the energy consumption is reduced and the industrial production is facilitated; and the obtained europium-doping calcium titanate fluorescent powder has the advantages of good dispersibility, difficulty in agglomeration, spheroidal structure and good application prospect.
Description
Technical field
The invention belongs to the preparation field of calcium titanate fluorescent material, particularly a kind of preparation method of europium-doped calcium titanate fluorescent material.
Background technology
White light LEDs is as a kind of new green environment protection type solid light source, and being described as 21 century has the new type light source of development potentiality most, in the numerous areas prospect that all has a very wide range of applications, and as mobile phone, the backlight of computer etc.
White light LEDs can utilize led chip to cooperate fluorescent material to realize, is YAG:Ce fluorescent material and use maximum fluorescent material at present, and its thermostability is relatively poor, and colour rendering index is low, is difficult to satisfy the needs of high-quality illumination.In order to address this problem, the fluorescent material that the Heat stability is good colour rendering index is high has been subjected to extensive concern.For example Jia etc. is at the Sr of Solid StateCommunication.Vol.126 (2003) pp.153～157 reports
1-xCa
xTiO
3: Pr
3+Fluorescent material and Eric etc. are at the CaTiO of Alloys andComoouds.Vol.374 (2004) pp.202～206 reports
3: Pr
3+Fluorescent material has solved the thermostability and the low problem of luminous index of fluorescent material, however the synthesis temperature of these fluorescent material too high (1350 ℃).Mazzb etc. have reported in OpticalMaterials.Vol.32 (2010) pp.990～997 and have utilized hydrothermal method to synthesize CaTiO
3: Eu
3+Fluorescent material, they have synthesized fluorescent material under lower temperature, but the fluorescent powder grain size that this method obtains is big and become block accumulation, and it is serious to reunite, and is difficult to realize the high quality encapsulation of fluorescent material.Sun etc. have reported CaTiO in Alloys and Compounds.Vol.493 (2010) pp.561～564
3: Eu
3+The fluorescent material of the nucleocapsid structure of parcel silica dioxide granule, its luminescent properties is better, and synthesis temperature is lower, but luminous efficiency remains further to be improved.
Therefore, seek at present and a kind ofly guaranteeing that synthesis temperature is low under the prerequisite of better luminescent properties, the granule-morphology rule, the fluorescent material of good dispersity becomes the severe challenge that we face.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of europium-doped calcium titanate fluorescent material, and this method is simple, and cost is low, and gained europium-doped calcium titanate fluorescent material gets good dispersity, is difficult for reuniting, and has ball-like structure.
The preparation method of a kind of europium-doped calcium titanate fluorescent material of the present invention comprises:
(1) at room temperature, with positive four butyl esters of metatitanic acid be scattered in the dehydrated alcohol solution, ammonia soln is added in metatitanic acid positive four butyl acetate solutions obtains white precipitate by volume at 0.5～0.8: 1, washing precipitation gets precursor;
(2) above-mentioned precursor is scattered in the mixing solutions of ethylene glycol, quadrol, continues to stir formation presoma suspension;
(3) lime acetate, europium nitrate and sodium hydroxide are dissolved in deionized water and splashing in the above-mentioned presoma suspension respectively, add polyoxyethylene glycol again, pour reactor after the stirring into, be warming up to 180～220 ℃ of reaction 8～12h; Wherein, the mol ratio of positive four butyl esters of lime acetate, europium nitrate and metatitanic acid is 2.6～3: 0.01～0.1: 1, the mol ratio of sodium hydroxide and calcium ion is 4.5～7: 1, the volume of deionized water is 1/30～1/10 of ethylene glycol and a quadrol cumulative volume, and the volume of polyoxyethylene glycol is 1/40～1/10 of middle ethylene glycol of step (2) and a quadrol cumulative volume;
(4) after reaction finishes, be cooled to room temperature, the washing desciccate, promptly.
Ammonia soln concentration in the described step (1) is 1～3mol/L, and the concentration of positive four butyl acetate solutions of metatitanic acid is 0.4～0.8mol/L.
The volume ratio of ethylene glycol and quadrol is 0.8～1.2: 1 in ethylene glycol in the described step (2), the quadrol mixing solutions.
Molecular weight polyethylene glycol in the described step (4) is 200～600.
Washing in the described step (4) is for using ethanol, hydrochloric acid soln and deionized water wash 2～5 times successively, and drying is in 60～80 ℃ of drying 12～20h.
The pH value of the hydrochloric acid soln in the described step (4) is 1～3.
The present invention is by positive four butyl esters of metatitanic acid, ethanol, and the white precipitate that generates in ammonia soln is as precursor; With quadrol and ethylene glycol is solvent, and polyoxyethylene glycol is a dispersion agent, precursor is dispersed in forms suspension in the solvent earlier, and again with lime acetate, europium nitrate mixed solution, sodium hydroxide solution, polyoxyethylene glycol splash into the formation mixed solution successively.Elder generation is dispersed in the precursor precipitation can make calcium ion in the solvent, europium ion is easier and the precursor uniform mixing.Pour above-mentioned mixed solution into reactor, be warming up to certain temperature and be incubated for some time after scouring drying and obtain CaTiO
3: Eu
3+Fluorescent material.
Beneficial effect
(1) preparation method of the present invention is simple, and cost is low, and required production unit is simple, and temperature of reaction is low, reduces energy consumption, is easy to suitability for industrialized production;
(2) gained europium-doped calcium titanate fluorescent material gets good dispersity, is difficult for reuniting, and has ball-like structure, has a good application prospect.
Description of drawings
Fig. 1 is europium-doped calcium titanate (CaTiO
3: Eu
3+) X-ray diffractogram of fluorescent material;
Fig. 2 is europium-doped calcium titanate (CaTiO
3: Eu
3+) stereoscan photograph of fluorescent material;
Fig. 3 is europium-doped calcium titanate (CaTiO
3: Eu
3+) fluorescence spectrum of fluorescent material.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
Get positive four butyl esters of metatitanic acid of 1.74ml, it is scattered in the 10ml dehydrated alcohol, it is white precipitate that the ammonia soln of the 3mol/L by dripping 10ml makes its total overall reaction, with deionized water centrifuge washing 3 times.Again above-mentioned precursor is added the mixed solution of 15ml ethylene glycol, 15ml quadrol and stir 50min and make in its abundant dispersing and mixing liquid, with 2.275g lime acetate, 0.036g europium nitrate dissolving mixed solution, 3.0g sodium hydroxide solution, 1ml Macrogol 200 later, at revolution is to stir 50min under the 200r/min, makes gained solution shape suspension.Above-mentioned reactant is poured in the reactor that volume is 100ml, behind insulation 12h under 180 ℃, be cooled to room temperature then.Wash centrifugal collection product, wash 2 times with ethanol earlier, wash 3 times, with product dry 12h under 80 ℃, obtain CaTiO at last again with pH=1 hydrochloric acid soln washing 2 times, and then with deionized water
3: Eu
3+Fluorescent material.Fig. 1 is the X-ray diffractogram of present embodiment synthetic fluorescent material, and as can be seen: diffraction peak is consistent with the diffraction peak of the calcium titanate of cube phase, does not find other diffraction peak, illustrates not contain other dephasign, and Fig. 2 is CaTiO
3: Eu
3+The fluorescent material stereoscan photograph, as can be seen: synthetic fluorescent material good dispersity, and have ball-like structure, the diameter of ball is 2～3 μ m.Fig. 3 is fluorescence spectrum figure, and as can be seen: the excitation wavelength of synthetic fluorescent material is 398.4nm, and emission wavelength is 617.6nm.
Embodiment 2
Get positive four butyl esters of metatitanic acid of 1.78ml, it is scattered in the 12ml dehydrated alcohol, it is white precipitate that the ammonia soln of the 2mol/L by dripping 15ml makes its total overall reaction, with deionized water centrifuge washing 4 times.Again above-mentioned precursor is added the mixed solution of 17ml ethylene glycol, 20ml quadrol and stir 40min and make in its abundant dispersing and mixing liquid, with 2.448g lime acetate, 0.104g europium nitrate dissolving mixed solution, 3.5g sodium hydroxide solution, 2ml poly(oxyethylene glycol) 400 later, at revolution is to stir 40min under the 300r/min, makes gained solution shape suspension.Above-mentioned reactant is poured in the reactor that volume is 100ml, after keeping 10 hours under 200 ℃, be cooled to room temperature then.Wash centrifugal collection product, wash 3 times with ethanol earlier, wash 3 times, with product dry 15h under 70 ℃, obtain CaTiO at last again with pH=2 hydrochloric acid soln washing 3 times, and then with deionized water
3: Eu
3+Fluorescent material.X-ray diffractogram shows that product is mainly CaTiO
3Phase, stereoscan photograph show synthetic fluorescent material good dispersity, and have ball-like structure, and the diameter of ball is 2～3 μ m.Fluorescence spectrum figure shows that the excitation wavelength of synthetic fluorescent material is 398.4nm, and emission wavelength is 617.6nm.
Embodiment 3
Get positive four butyl esters of metatitanic acid of 1.85ml, it is scattered in the 15ml dehydrated alcohol, it is white precipitate that the ammonia soln of the 1mol/L by dripping 20ml makes its total overall reaction, with deionized water centrifuge washing 5 times.Above-mentioned precursor being added the mixed solution of 28ml ethylene glycol, 25ml quadrol again and stirring 30min is well dispersed in the mixed solution it, with 2.673g lime acetate, 0.202g europium nitrate dissolving mixed solution, 3.8g sodium hydroxide solution, 2ml Polyethylene Glycol-600 later, at revolution is to stir 20min under the 500r/min, makes gained solution shape suspension.Above-mentioned reactant is poured in the reactor that volume is 100ml, after keeping 8 hours under 220 ℃, be cooled to room temperature then.Wash centrifugal collection product, wash 3 times with ethanol earlier, wash 5 times, with product dry 20h under 60 ℃, obtain CaTiO at last again with pH=3 hydrochloric acid soln washing 4 times, and then with deionized water
3: Eu
3+Fluorescent material.X-ray diffractogram shows that product is mainly no dephasign, and stereoscan photograph shows synthetic fluorescent material good dispersity, and has ball-like structure, and the diameter of ball is 2～3 μ m.Fluorescence spectrum figure shows that the excitation wavelength of synthetic fluorescent material is 398.4nm, and emission wavelength is 617.6nm.
Claims (6)
1. the preparation method of an europium-doped calcium titanate fluorescent material comprises:
(1) at room temperature, with positive four butyl esters of metatitanic acid be scattered in the dehydrated alcohol solution, ammonia soln is added in metatitanic acid positive four butyl acetate solutions obtains white precipitate by volume at 0.5～0.8: 1, washing precipitation gets precursor;
(2) above-mentioned precursor is scattered in the mixing solutions of ethylene glycol, quadrol, continues to stir formation presoma suspension;
(3) lime acetate, europium nitrate and sodium hydroxide are dissolved in deionized water and splashing in the above-mentioned presoma suspension respectively, add polyoxyethylene glycol again, pour reactor after the stirring into, be warming up to 180～220 ℃ of reaction 8～12h; Wherein, the mol ratio of positive four butyl esters of lime acetate, europium nitrate and metatitanic acid is 2.6～3: 0.01～0.1: 1, the mol ratio of sodium hydroxide and calcium ion is 4.5～7: 1, the volume of deionized water is 1/30～1/10 of ethylene glycol and a quadrol cumulative volume, and the volume of polyoxyethylene glycol is 1/40～1/10 of middle ethylene glycol of step (2) and a quadrol cumulative volume;
(4) after reaction finishes, be cooled to room temperature, the washing desciccate, promptly.
2. the preparation method of a kind of europium-doped calcium titanate fluorescent material according to claim 1 is characterized in that: the ammonia soln concentration in the described step (1) is 1～3mol/L, and the concentration of positive four butyl acetate solutions of metatitanic acid is 0.4～0.8mol/L.
3. the preparation method of a kind of europium-doped calcium titanate fluorescent material according to claim 1 is characterized in that: the volume ratio of ethylene glycol and quadrol is 0.8～1.2: 1 in the ethylene glycol in the described step (2), the quadrol mixing solutions.
4. the preparation method of a kind of europium-doped calcium titanate fluorescent material according to claim 1 is characterized in that: the molecular weight polyethylene glycol in the described step (4) is 200～600.
5. the preparation method of a kind of europium-doped calcium titanate fluorescent material according to claim 1 is characterized in that: the washing in the described step (4) is for using ethanol, hydrochloric acid soln and deionized water wash 2～5 times successively, and drying is in 60～80 ℃ of drying 12～20h.
6. the preparation method of a kind of europium-doped calcium titanate fluorescent material according to claim 4 is characterized in that: the pH value of the hydrochloric acid soln in the described step (4) is 1～3.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105016379A (en) * | 2015-07-27 | 2015-11-04 | 昆明理工大学 | Method for preparing calcium metatitanate |
| CN106701072A (en) * | 2016-12-22 | 2017-05-24 | 中国科学院合肥物质科学研究院 | Europium-doped calcium titanate nano cube fluorescent powder and preparation method thereof |
| CN109201088A (en) * | 2018-11-02 | 2019-01-15 | 扬州工业职业技术学院 | A kind of Eu3+, Se codope TiO2/ GO material and its application in photocatalysis |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921588A (en) * | 2010-06-23 | 2010-12-22 | 东华大学 | Method for preparing europium-doped calcium titanate CaTiO3: Eu3 plus fluorescent powder by solvent-thermal method |
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| CN101921588A (en) * | 2010-06-23 | 2010-12-22 | 东华大学 | Method for preparing europium-doped calcium titanate CaTiO3: Eu3 plus fluorescent powder by solvent-thermal method |
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| Title |
|---|
| 《中国优秀硕士学位论文全文数据库 信息科技辑》 20100415 贾乃涛 YAG:Ce 荧光粉的制备" 第33页第4.2节，第51页第3段 1-3,5 , * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105016379A (en) * | 2015-07-27 | 2015-11-04 | 昆明理工大学 | Method for preparing calcium metatitanate |
| CN106701072A (en) * | 2016-12-22 | 2017-05-24 | 中国科学院合肥物质科学研究院 | Europium-doped calcium titanate nano cube fluorescent powder and preparation method thereof |
| CN106701072B (en) * | 2016-12-22 | 2019-02-19 | 中国科学院合肥物质科学研究院 | Europium-doped calcium titanate nano square fluorescent powder and preparation method thereof |
| CN109201088A (en) * | 2018-11-02 | 2019-01-15 | 扬州工业职业技术学院 | A kind of Eu3+, Se codope TiO2/ GO material and its application in photocatalysis |
| CN109201088B (en) * | 2018-11-02 | 2021-06-25 | 扬州工业职业技术学院 | Eu (Eu)3+Se co-doping of TiO2/GO material and its application in photocatalysis |
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