CN101921588B - Method for preparing europium-doped calcium titanate CaTiO3: Eu3 plus fluorescent powder by solvent-thermal method - Google Patents
Method for preparing europium-doped calcium titanate CaTiO3: Eu3 plus fluorescent powder by solvent-thermal method Download PDFInfo
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Abstract
The invention relates to a method for preparing europium-doped calcium titanate CaTiO3: Eu3 plus fluorescent powder by the solvent-thermal method, which comprises the following steps: (1) dissolving tetrabutyl titanate in anhydrous ethanol at room temperature, simultaneously carrying out magnetic stirring, dripping ammonia solution into the mixed solution, obtaining white precipitate, centrifugating and washing a product; (2) mixing and stirring ethylenediamine, ethanolamine, deionized water, calcium acetate, europium nitrate, sodium hydroxide and polyethylene glycol, pouring the solution and the product into a reaction kettle, increasing the temperature to 180-220 DEG C and carrying out reaction for 8-12h; and (3) collecting the reaction product in a centrifugation way after the reaction is finished, respectively washing the product with acid and deionized water, drying, and obtaining the CaTiO3: Eu3 plus fluorescent powder. The preparation method has simple process, low synthesis temperature and is applicable to industrial production, and the prepared fluorescent powder has the advantages of good dispersivity, high chemical stability, high crystal phase purity, small size and hollow pipe-like structure.
Description
Technical field
The invention belongs to CaTiO
3Preparation field, particularly a kind of solvent-thermal method prepares europium-doped calcium titanate CaTiO
3: Eu
3+The method of fluorescent material.
Background technology
Fluorescent material as the core material of white light LEDs all is the hot research problem of lighting field all the time, and the performance of fluorescent material also directly affects the development of white light LEDs.The preparation method of fluorescent material is a lot, and main synthetic method has at present: high-temperature solid phase reaction method, sol-gel method, homogeneous coprecipitation method, low-temperature combustion synthesis, hydrothermal synthesis method, Microwave Radiation Synthesis Method, polymer-network gel method, surface diffusion method etc.Yttrium aluminum garnet (yttrium aluminum garnet, the YAG) fluorescent material that Japan Ri Ya chemical company at first developed in 1996 with gold-tinted series cooperates blue-ray LED to obtain high efficiency white light source.
In recent years, the scientific research personnel has carried out large quantity research to preparation, the luminescent properties of yttrium aluminum garnet series phosphor powder.This fluorescent material relies on satisfactory stability and has obtained using very widely with the matched well of corresponding led chip, and commercialization.But the design of this class blue-light LED chip collocation gold-tinted fluorescent material exists very large defective, and at first this fluorescent material is by the high-temperature solid phase reaction method preparation, although high-temperature solid phase reaction method is synthetizing phosphor powder to be used the earliest, maximum a kind of method.But that a major defect of this method is preparation temperature is high, reaction not exclusively, contain a small amount of original solid material in the product.Secondly, along with the increase of duration of service, the problem of aging of chip will cause the light blue shift that sends, and the hybrid light source that finally makes the light that its and fluorescent material sends is indigo plant partially, and colour rendering index is reduced greatly.Zhou etc. are at Alloys and Compounds.2004, and 375 (1): reported a kind of Y by the wet chemistry method preparation in 93
3Al
5O
12: RE
3+(RE:Eu, Dy) fluorescent material can effectively be simplified synthesis technique, but still can't solve the aging series of problems that causes of chip.And the research of the high efficiency red phosphor powder that can effectively be excited by UV and nearly UV light can solve luminous colder this problem.The red fluorescence powder aspect, Zhuan Weidong etc. are at China rare earth journal 2004,22 (6): 854 have reported that a kind of divalent europium activates the red fluorescence powder of alkaline earth transition metal complex sulfide.Divalent europium activates sulfide (Sr, Ca) S:Eu
2+Excite the long 600nm of being of lower emission spike at 460nm.But this fluorescent material poor stability, easy deliquescence must coat processing.As seen, still there is at present the problem of many sternnesses in the fluorescent material research field, such as, the fluorescent material that light conversion efficiency and thermal stability are good particularly can extremely be lacked by the high efficiency red phosphor powder that nearly UV light effectively excites, and extremely needs.Because the luminous efficiency of the present red fluorescent powder for white radiation LED of developing is low, can not meet the demands, this just needs us to seek new and effective red fluorescent powder for white radiation LED.
Summary of the invention
Technical problem to be solved by this invention provides a kind of solvent-thermal method and prepares europium-doped calcium titanate CaTiO
3: Eu
3+The method of fluorescent material, this preparation method's technique is simple, and synthesis temperature is low, is easy to suitability for industrialized production, prepared CaTiO
3: Eu
3+The fluorescent material good dispersity, chemical stability is high, crystalline phase is pure, size is little, and is hollow tubular structures.
A kind of solvent-thermal method of the present invention prepares europium-doped calcium titanate CaTiO
3: Eu
3+The method of fluorescent material comprises:
(1) at room temperature, tetrabutyl titanate is dissolved in the dehydrated alcohol, carries out simultaneously magnetic agitation, 0.1～1mol/L ammonia soln is slowly splashed in the mixed solution of dehydrated alcohol and tetrabutyl titanate, obtain white precipitate, centrifugal, wash to get product;
(2) at room temperature, with quadrol, thanomin, deionized water, calcium acetate, europium nitrate, sodium hydroxide and polyoxyethylene glycol mix and blend, add afterwards above-mentioned product, be warming up to 180～220 ℃, reaction 8～12h;
(3) use centrifugal mode collecting reaction product after reaction finishes, the hydrochloric acid washing reaction product with pH=2～3 re-uses the deionized water wash product, at 50～80 ℃ of lower dry 20～28h, obtains CaTiO subsequently
3: Eu
3+Fluorescent material;
In the above-mentioned steps, the volume ratio of tetrabutyl titanate and dehydrated alcohol is 1/20～1/5, the mol ratio of tetrabutyl titanate and ammoniacal liquor is 1/4～1/6, calcium acetate, the mol ratio of europium nitrate and tetrabutyl titanate is 3: 0: 1～2.7: 0.3: 1, the sodium hydroxide quality is 125～200% of calcium acetate quality, the volume ratio of thanomin and quadrol is 1: 1, the deionized water volume is 8～10% of thanomin and quadrol cumulative volume, thanomin, the cumulative volume of quadrol and deionized water is 1/2～3/4 of reactor volume, the polyoxyethylene glycol volume is 1/50～1/20 of thanomin and quadrol cumulative volume, and the mass ratio of calcium acetate and thanomin is 1/15～1/5.
Stirring velocity in the described step (2) is 300～500 rev/mins, and churning time is 20～40min.
CaTiO in the described step (3)
3: Eu
3+Fluorescent material is hollow tubular structures.
The present invention is by adopting solvent-thermal method to prepare CaTiO
3: Eu
3+Fluorescent material, solvent-thermal method can be strict the control reactant between ratio, be difficult for to generate impurity phase, obtain the high reaction product of purity, and because dielectricity and the viscosity of thanomin and quadrol, synthetic powder size is little, is evenly distributed.The rare earth doped chemical stability that can guarantee fluorescent material take calcium titanate as matrix.
Beneficial effect
(1) this preparation method's technique is simple, and synthesis temperature is low, is easy to suitability for industrialized production;
(2) use the prepared CaTiO of the method
3: Eu
3+The fluorescent material good dispersity, chemical stability is high, crystalline phase is pure, size is little, and is hollow tubular structures.
Description of drawings
Fig. 1 is europium-doped calcium titanate CaTiO
3: Eu
3+The X-ray diffractogram of fluorescent material;
Fig. 2 is europium-doped calcium titanate CaTiO
3: Eu
3+The stereoscan photograph of fluorescent material;
Fig. 3 is europium-doped calcium titanate CaTiO
3: Eu
3+The 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.
Measure positive four butyl esters of metatitanic acid of 1.716ml, be dissolved in the 10ml dehydrated alcohol, it is the titanium hydroxide precipitation that the ammonia soln ammoniacal liquor of the 0.5mol/L by dripping 50ml makes its total overall reaction, through 3 washings, removes unnecessary ammonium ion.The europium nitrate, 3.3g sodium hydroxide, the 1ml polyoxyethylene glycol that add 25ml thanomin, 25ml quadrol, 5ml deionized water, 2.6163g calcium acetate, 0.05069g are to stir 30min under the 350r/min at revolution, so that all solutes disperse fully again.Mentioned solution and throw out are poured in the reactor that volume is 80ml, then put into baking oven, at 180 ℃ of lower maintenances 14 hours, then cool to room temperature.Centrifugal collection product after reaction finishes, and with the hydrochloric acid washed product of deionized water and pH=2～3, then product is descended dry 24h at 60 ℃,, obtain CaTiO
3: Eu
3+Fluorescent material.
Fig. 1 is the X-ray diffractogram of the synthetic fluorescent material of present embodiment, can find out: diffraction peak is consistent with the diffraction peak of the calcium titanate of Emission in Cubic, discovery belongs to the diffraction peak of other oxide compound of calcium, illustrate and do not contain impurity phase, analyse and compare by XRD data analysis software (JADE 5.0), the result shows the CaTiO that has synthesized the quadrature phase
3: Eu
3+Fluorescent material.
Fig. 2 is CaTiO
3: Eu
3+The stereoscan photograph of fluorescent material, can find out: synthetic fluorescent material good dispersity is hollow tubular structures.
Fig. 3 is the fluorescence spectrum under the 398.4nm wavelength light of fluorescent material excites, and can find out: synthetic fluorescent material has higher emissive porwer under near ultraviolet excitation.
Measure positive four butyl esters of metatitanic acid of 1.716ml, be dissolved in the 20ml dehydrated alcohol, making its total overall reaction by the 1mol/L ammoniacal liquor that drips 25ml is the titanium hydroxide precipitation, through 3 washings, removes unnecessary ammonium ion.The europium nitrate, 3.8g sodium hydroxide, the 1.4ml polyoxyethylene glycol that add 20ml thanomin, 20ml quadrol, 3.5ml deionized water, 2.5370g calcium acetate, 0.2028g are to stir 25min under the 400r/min at revolution, so that all solutes disperse fully again.Mentioned solution and throw out are poured in the reactor that volume is 80ml, then put into baking oven, at 200 ℃ of lower maintenances 12 hours, then cool to room temperature.Centrifugal collection product after reaction finishes, and with the hydrochloric acid washed product of deionized water and pH=2～3, then product is descended dry 28h at 60 ℃, obtain CaTiO
3: Eu
3+Fluorescent material.
X ray test is the result show: diffraction peak is consistent with the diffraction peak of the calcium titanate of Emission in Cubic, discovery belongs to the diffraction peak of other oxide compound of calcium, illustrate and do not contain impurity phase that analyse and compare by XRD data analysis software (JADE 5.0), the result shows the CaTiO that has synthesized the quadrature phase
3: Eu
3+Fluorescent material.
Scanning electron microscopic observation shows: synthetic fluorescent material good dispersity is hollow tubular structures.
Adopt the 398.4nm wavelength light to excite the fluorescence spectrum test of test fluorescent material to show: synthetic fluorescent material has higher emissive porwer under near ultraviolet excitation.
Embodiment 3
Measure positive four butyl esters of metatitanic acid of 1.716ml, be dissolved in the 30ml dehydrated alcohol, making its total overall reaction by the 3mol/L ammoniacal liquor that drips 8ml is the titanium hydroxide precipitation, through 3 washings, removes unnecessary ammonium ion.The europium nitrate, 4.7g sodium hydroxide, the 1ml polyoxyethylene glycol that add 15ml thanomin, 15ml quadrol, 3ml deionized water, 2.3780g calcium acetate, 0.5069g are to stir 20min under the 500r/min at revolution, so that all solutes disperse fully again.Mentioned solution and throw out are poured in the reactor that volume is 80ml, then put into baking oven, at 220 ℃ of lower maintenances 10 hours, then cool to room temperature.Centrifugal collection product after reaction finishes, and with the hydrochloric acid washed product of deionized water and pH=2～3, then with product at 80 ℃ of lower 20h of drying, obtain CaTiO
3: Eu
3+Fluorescent material.
X ray test is the result show: diffraction peak is consistent with the diffraction peak of the calcium titanate of Emission in Cubic, discovery belongs to the diffraction peak of other oxide compound of calcium, illustrate and do not contain impurity phase that analyse and compare by XRD data analysis software (JADE 5.0), the result shows the CaTiO that has synthesized the quadrature phase
3: Eu
3+Fluorescent material.
Scanning electron microscopic observation shows: synthetic fluorescent material good dispersity is hollow tubular structures.
Adopt the 398.4nm wavelength light to excite the fluorescence spectrum test of test fluorescent material to show: synthetic fluorescent material has higher emissive porwer under near ultraviolet excitation.
Claims (3)
1. a solvent-thermal method prepares europium-doped calcium titanate CaTiO
3: Eu
3+The method of fluorescent material comprises:
(1) at room temperature, tetrabutyl titanate is dissolved in the dehydrated alcohol, carries out simultaneously magnetic agitation, 0.1～1mol/L ammonia soln is slowly splashed in the mixed solution of dehydrated alcohol and tetrabutyl titanate, obtain white precipitate, centrifugal, wash to get product;
(2) with quadrol, thanomin, deionized water, calcium acetate, europium nitrate, sodium hydroxide and polyoxyethylene glycol mix and blend, add afterwards above-mentioned product, be warming up to 180 ~ 220 ° of C, reaction 8 ~ 12h;
(3) use centrifugal mode collecting reaction product after reaction finishes, the hydrochloric acid washing reaction product with pH=2 ~ 3 re-uses the deionized water wash product, and dry 20 ~ 28h under 50 ~ 80 ° of C obtains CaTiO subsequently
3: Eu
3+Fluorescent material;
In the above-mentioned steps, the volume ratio of tetrabutyl titanate and dehydrated alcohol is 1/20 ~ 1/5, and the mol ratio of tetrabutyl titanate and ammoniacal liquor is 1/4 ~ 1/6; The mol ratio of calcium acetate, europium nitrate and tetrabutyl titanate is 3:0:1 ~ 2.7:0.3:1, the sodium hydroxide quality is 125 ~ 200% of calcium acetate quality, the volume ratio of thanomin and quadrol is 1:1, the deionized water volume is 8 ~ 10% of thanomin and quadrol cumulative volume, the cumulative volume of thanomin, quadrol and deionized water is 1/2 ~ 3/4 of reactor volume, the polyoxyethylene glycol volume is 1/50 ~ 1/20 of thanomin and quadrol cumulative volume, and the mass ratio of calcium acetate and thanomin is 1/15 ~ 1/5.
2. a kind of solvent-thermal method according to claim 1 prepares europium-doped calcium titanate CaTiO
3: Eu
3+The method of fluorescent material is characterized in that: the stirring velocity in the described step (2) is 300 ~ 500 rev/mins, and churning time is 20 ~ 40min.
3. a kind of solvent-thermal method according to claim 1 prepares europium-doped calcium titanate CaTiO
3: Eu
3+The method of fluorescent material is characterized in that: the CaTiO in the described step (3)
3: Eu
3+Fluorescent material is hollow tubular structures.
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| CN102242400B (en) * | 2011-06-29 | 2013-06-05 | 浙江大学 | Method for preparing monocrystalline CaTiO3 dendrite |
| 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 |
| CN111180699B (en) * | 2020-01-02 | 2021-07-09 | 南京邮电大学 | Titanate/carbon composite material and preparation method and application thereof |
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Non-Patent Citations (1)
| Title |
|---|
| Fu Jiapeng."Highly luminescent red light phosphor CaTiO(3):Eu(3+) under near-ultraviolet excitation".《JOURNAL OF LUMINESCENCE》.2010,第231页第4段. * |
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