CN102212365B - 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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- CN102212365B CN102212365B CN 201110091323 CN201110091323A CN102212365B CN 102212365 B CN102212365 B CN 102212365B CN 201110091323 CN201110091323 CN 201110091323 CN 201110091323 A CN201110091323 A CN 201110091323A CN 102212365 B CN102212365 B CN 102212365B
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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-doping calcium titanate fluorescent powder.
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 such 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 at present maximum fluorescent material, 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 subject to extensive concern.Such as the Sr at Solid StateCommunication.Vol.126 (2003) pp.153～157 reports such as Jia
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 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 the method obtains is large 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 under a kind of prerequisite guaranteeing better luminescent properties, synthesis temperature is low, the granule-morphology rule, and 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-doping calcium titanate fluorescent powder, and the method is simple, and cost is low, and the gained europium-doping calcium titanate fluorescent powder gets good dispersity, is difficult for reuniting, and has ball-like structure.
The preparation method of a kind of europium-doping calcium titanate fluorescent powder of the present invention comprises:
(1) at room temperature, positive four butyl esters of metatitanic acid are scattered in the dehydrated alcohol to get solution, ammonia soln is added in positive four butyl acetate solutions of metatitanic acid and 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 respectively deionized water and splashing in the above-mentioned presoma suspension, add again polyoxyethylene glycol, 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 quadrol cumulative volume, and the volume of polyoxyethylene glycol is 1/40～1/10 of the middle ethylene glycol of step (2) and quadrol cumulative volume;
(4) after reaction finishes, be cooled to room temperature, the washing desciccate, and get final product.
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 successively ethanol, hydrochloric acid soln and deionized water wash 2～5 times, 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; Take quadrol and ethylene glycol as solvent, polyoxyethylene glycol is dispersion agent, precursor is dispersed in forms suspension in the solvent first, and again with lime acetate, europium nitrate mixed solution, sodium hydroxide solution, polyoxyethylene glycol splash into the formation mixed solution successively.First precursor precipitation is dispersed in and can makes calcium ion in the solvent, europium ion is easier evenly mixes with precursor.Pour above-mentioned mixed solution into reactor, the washing drying obtains CaTiO after being warming up to certain temperature and being incubated for some time
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) the gained europium-doping calcium titanate fluorescent powder 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 for explanation the present invention 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 limited range 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, be to stir 50min under the 200r/min at revolution, make gained solution shape suspension.Above-mentioned reactant is poured in the reactor that volume is 100ml, then behind 180 ℃ of lower insulation 12h, be cooled to room temperature.Wash centrifugal collection product, wash 2 times with ethanol first, wash 3 times again with pH=1 hydrochloric acid soln washing 2 times, and then with deionized water, with product dry 12h under 80 ℃, obtain CaTiO at last
3: Eu
3+Fluorescent material.Fig. 1 is the X-ray diffractogram of the synthetic fluorescent material of present embodiment, and can find out: diffraction peak is consistent with the diffraction peak of the calcium titanate of Emission in Cubic, does not find other diffraction peak, illustrates not contain other dephasign, and Fig. 2 is CaTiO
3: Eu
3+The fluorescent material stereoscan photograph, can find out: 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, can find out: 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, be to stir 40min under the 300r/min at revolution, make gained solution shape suspension.Above-mentioned reactant is poured in the reactor that volume is 100ml, then after 10 hours, be cooled to room temperature 200 ℃ of lower maintenances.Wash centrifugal collection product, wash 3 times with ethanol first, wash 3 times again with pH=2 hydrochloric acid soln washing 3 times, and then with deionized water, with product dry 15h under 70 ℃, obtain CaTiO at last
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, be to stir 20min under the 500r/min at revolution, make gained solution shape suspension.Above-mentioned reactant is poured in the reactor that volume is 100ml, then after 8 hours, be cooled to room temperature 220 ℃ of lower maintenances.Wash centrifugal collection product, wash 3 times with ethanol first, wash 5 times again with pH=3 hydrochloric acid soln washing 4 times, and then with deionized water, with product dry 20h under 60 ℃, obtain CaTiO at last
3: Eu
3+Fluorescent material.X-ray diffractogram shows that product is mainly without 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-doping calcium titanate fluorescent powder comprises:
(1) at room temperature, positive four butyl esters of metatitanic acid are scattered in the dehydrated alcohol to get solution, with ammonia soln by volume 0.5 ~ 0.8:1 add in positive four butyl acetate solutions of metatitanic acid and obtain white precipitate, washing precipitation gets presoma;
(2) above-mentioned presoma 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 respectively deionized water and splashing in the above-mentioned presoma suspension, add again polyoxyethylene glycol, pour reactor after the stirring into, be warming up to 180 ~ 220 ° of C 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 quadrol cumulative volume, and the volume of polyoxyethylene glycol is 1/40 ~ 1/10 of the middle ethylene glycol of step (2) and quadrol cumulative volume;
(4) after reaction finishes, be cooled to room temperature, the washing desciccate, and get final product.
2. the preparation method of a kind of europium-doping calcium titanate fluorescent powder according to claim 1, it is characterized in that: the ammonia soln concentration in the described step (1) is 1 ~ 3mol/L, 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-doping calcium titanate fluorescent powder according to claim 1, it 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-doping calcium titanate fluorescent powder according to claim 1, it is characterized in that: the molecular weight polyethylene glycol in the described step (3) is 200 ~ 600.
5. the preparation method of a kind of europium-doping calcium titanate fluorescent powder according to claim 1 is characterized in that: the washing in the described step (4) is for using successively ethanol, hydrochloric acid soln and deionized water wash 2 ~ 5 times, and drying is in 60 ~ 80 ℃ of drying 12 ~ 20h.
6. the preparation method of a kind of europium-doping calcium titanate fluorescent powder according to claim 5, it is characterized in that: the pH value of the hydrochloric acid soln in the described step (4) is 1 ~ 3.
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| 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 |
| 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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|---|---|---|---|---|
| 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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Non-Patent Citations (2)
| Title |
|---|
| 贾乃涛.YAG:Ce 荧光粉的制备".《中国优秀硕士学位论文全文数据库 信息科技辑》.2010,第33页第4.2节，第51页第3段. |
| 贾乃涛.YAG:Ce 荧光粉的制备".《中国优秀硕士学位论文全文数据库 信息科技辑》.2010,第33页第4.2节,第51页第3段. * |
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