CN100339460C - Preparation method of silicate luminous body for converting blue light to white light - Google Patents
Preparation method of silicate luminous body for converting blue light to white light Download PDFInfo
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- CN100339460C CN100339460C CNB2005101222537A CN200510122253A CN100339460C CN 100339460 C CN100339460 C CN 100339460C CN B2005101222537 A CNB2005101222537 A CN B2005101222537A CN 200510122253 A CN200510122253 A CN 200510122253A CN 100339460 C CN100339460 C CN 100339460C
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- preparation
- europium
- strontium
- fluor
- fluophors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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Abstract
The present invention provides an aerosol preparation method for silicate fluophors converting and synthesizing blue light into white light, which belongs to the technical field of photoelectric materials. The method is characterized in that silicon dioxide particles in a nanometer dimension are used as pre-bury crystal seed, and the silicon dioxide particles are peptized by using weak acid and added with a small amount of polyvinyl alcohol; the silicon dioxide particles and a compound of strontium and europium are prepared into uniform solution according to a metering proportion and then atomized to evaporate water in liquid drops in the process of flight, and thus, the spherical dried gel particles with uniformly distributed components are formed; reduction thermal decomposition is carried out on the gel particles, and then high-purity spherical strontium silicate fluophors adulterated with europium with uniformly distributed components can be obtained. The method combines the advantages of a liquid phase method, a sol-gel method and a spraying thermal decomposition method; the fluophors are solid spheres of which the size is a plurality of microns to scores of nanometers, ball milling of the fluophors is not needed, and the method is suitable for mass production; the fluophors convert blue light into orange light and then synthesize the orange light into white light.
Description
[technical field]
The invention belongs to the photoelectric material technical field, especially provide a kind of blue light of mixing europium to change the aerosol preparation method of the silicate phosphor of synthesize white light.
[background technology]
White light-emitting diodes (LED) in the existing solid-state illumination technology is by cerium-doped yttrium aluminum garnet (YAG, Y
3Al
5O
12: Ce
3+) yellow fluorescence of fluor and the blue light of LED formation white light, the glow color of device changes with the variation of driving voltage and fluorescent coating thickness, and color reducibility is poor, and colour rendering index is low.YAG with blue light (～465nm) excite produce orange light (～560nm), thereby synthesize white light, Eu
2+, Tb
3+And Mn
2+Adulterated alkaline earth metal silicate substrate fluorescent body is an important techniques replacement scheme.
Solid-phase synthesis is still the traditional method of preparation luminescent material so far, for example, adopts BaCO
3, SrCO
3, CaCO
3, MgO, SiO
2And Eu
2O
3Mix, add flux NH
4Cl, ball milling is 48 hours in the Virahol environment, vapor away Virahol in the air, carry out granulation, pre-burning is 4 hours in the muffle furnace under 600 ℃, forward to again in the tube furnace at reducing atmosphere, the 1200-1400 ℃ following several hrs that burns, after burning till material water flush away flux, again at 3 hours (Control of spectralproperties of strontium-alkaline earth-silicate-europium phosphors for LEDapplications of 1300 ℃ of following resinterings, J of the Electrochem.Soc., 152 (5) G382-G385,2005).This method exists that component is inhomogeneous, firing temperature is high, there are a series of limitation such as dephasign easily in product.
Adopt the spraying-pyrolytic technique of soluble salt (being generally the nitrate of each component in the fluor) solution developed in the luminescent material technology of preparing. main deficiency is, atomizing droplet is when the moisture rapid evaporation, during with follow-up burning till, light-emitting particles is damaged easily, is not easy to form spherical.
[summary of the invention]
The object of the present invention is to provide a kind of aerosol preparation method of silicate phosphor of blue light conversion synthesize white light.A kind of aerogel technology of imbedding the silica dioxide granule of nanoscale is in advance adopted in this invention, and feed composition is mixed, and can also make the thing of final fluor mutually pure, size and pattern be controlled easily.
The invention discloses a kind of aerosol preparation method of silicate phosphor of blue light conversion synthesize white light, it is characterized in that adopting silica dioxide granule as fluor matrix, carry out peptization with weak acid, and adding dispersion agent, after the soluble salt of strontium and europium is made into homogeneous solution, atomize, form spherical dry gel particle; This particle carries out the reduction heat decomposition reaction again, can obtain the strontium silicate fluor of europium doped.
Method of the present invention is made into silica gel solution earlier, be atomized into dry gel particle again, obtain the high pure spherical europium doping strontium silicate fluor of uniform component distribution at last through once-firing, compared with prior art have several big characteristics: 1) Lian Jia nano silicon had both been done the silicon source of product, also, prevent or reduce the generation of ghost fluor as xerogel and particle crystalline center; 2) material composition mixes on nanometer, atom, molecular scale level; 3) the fluor firing temperature reduces; 4) phosphor particle submicron or tens nanometer sizes no longer need ball milling operation in the past; 5) Zhi Bei fluor thermostability and chemical stability be than existing YAG height, the lower suitable expansion scale production of cost.Fluor converts orange light to through blue light, final synthesize white light.
[embodiment]
The aerosol preparation method of the silicate phosphor of blue light conversion synthesize white light of the present invention, the silica dioxide granule that adopts nanoscale is as pre-buried crystal seed, carry out peptization with weak acid, and adding paucidisperse agent, soluble salt with strontium and europium atomizes after being made into homogeneous solution by metering, water in the drop is evaporated in flight course, form the spherical dry gel particle of uniform component distribution.This particle carries out the reduction heat decomposition reaction again, can obtain the strontium silicate fluor of europium doped.Wherein:
The fluor matrix group becomes Sr
2SiO
4The silicon-dioxide of nanoscale is adopted in the silicon source of fluor, and purity is 99.9-99.99% (percent by weight), and size is the 5-40 nanometer.Use the distilled water dosing, control silicon-dioxide by weight: water=1: 20～40, peptization is made in pH=2～4.Strontium in the fluor composition adopts water-soluble nitrate or acetate, and the purity of salt 〉=99.99% (percent by weight) joins silicon dioxide gel by stoichiometric ratio.Add the compound of europium and strontium in the silicon dioxide gel, the compound of europium and strontium adopts water-soluble nitrate or acetate, purity 〉=99.99% (percent by weight), and quantity is by strontium: europium=1: 0.01～0.05 (atomic molar number).The dispersion agent that adds in the silicon dioxide gel is solid polyethylene alcohol or solid alkyl trimethyl class, and quantity is the 0.1-5% of colloidal sol gross weight.Adopt colloidal sol air atomizing method then, at 110 ℃～250 ℃ of compressed air temperature, dry air amount 100～300m
3/ h atomizes to the doped silicon oxide colloid under streams 1～2L/h, obtains dry gel particle.At last, the dry gel particle that obtains reaches 1000 ℃～1400 ℃ of temperature at weakly reducing atmosphere, carries out high temperature in time 2-4 hour and burns till, and the reducing atmosphere that burns till can adopt N
2+ H
2, a kind of in gac reduction, decomposed ammonia body or the coal gas.
Following example is unrestricted the present invention in order further to illustrate technological process feature of the present invention.
Example 1
According to silicon-dioxide: water (weight ratio)=1: 20 is size the SiO of 10 nanometer sizes
2Join in the distilled water, transfer pH=2 with a small amount of nitric acid, again according to Sr
2SiO
4Formula is calculated the strontium nitrate that adds theoretical amount, presses strontium: europium (atomic molar number)=add europium nitrate at 1: 0.01, in colloidal sol, add polyvinyl alcohol again, and the polyvinyl alcohol of adding is 0.1% of a colloidal sol gross weight, carries out mechanical stirring and becomes colloidal sol, colloidal sol left standstill 1 hour; The air atomizing parameter is set is: 110 ℃ of temperature ins, dry air amount 100m
3/ h, streams 2L/h obtains dry gel particle; Feeding flow in horizontal pipe furnace is the N of 2L/h
2+ 5%H
2(volume ratio) mixed gas after burning till 2 hours under 1000 ℃, obtains fluor, and granular size is 6 microns, and is spherical in shape.
Example 2
According to silicon-dioxide: water (weight ratio)=1: 30 is size the SiO of 20 nanometer sizes
2Join in the distilled water, transfer pH=3 with a small amount of nitric acid, again according to Sr
2SiO
4Formula calculate to add the strontium nitrate of theoretical amount, press strontium: europium (atomic molar number)=1: 0.03 adding europium nitrate, in colloidal sol, add polyvinyl alcohol again, the polyvinyl alcohol of adding be the colloidal sol gross weight O.5%, carry out mechanical stirring and become colloidal sol, colloidal sol left standstill 2 hours; The air atomizing parameter is set is: 150 ℃ of temperature ins, dry air amount 200m
3/ h, streams 2L/h obtains dry gel particle; With gac reduction, in 1200 ℃ of following high temperature elevator furnaces, burn till 3 hours after, obtain fluor, granular size is 3 microns, and is spherical in shape.
Example 3
According to silicon-dioxide: water (weight ratio)=1: 40 is size the SiO of 40 nanometer sizes
2Join in the distilled water, transfer pH=2.5 with a small amount of nitric acid, again according to Sr
2SiO
4Formula is calculated the strontium nitrate that adds theoretical amount, presses strontium: europium (atomic molar number)=add europium nitrate at 1: 0.04, in colloidal sol, add polyvinyl alcohol again, and the polyvinyl alcohol of adding is 0.8% of a colloidal sol gross weight, carries out mechanical stirring and becomes colloidal sol, colloidal sol left standstill 3 hours; The air atomizing parameter is set is: 200 ℃ of temperature ins, dry air amount 300m
3/ h, streams 2L/h obtains dry gel particle; Feeding flow in horizontal pipe furnace is the N of 2L/h
2+ 5%H
2(volume ratio) mixed gas after burning till 2 hours under 1300 ℃, obtains fluor, and granular size is 1 micron, and is spherical in shape.
Claims (11)
1. the preparation method of the silicate phosphor of blue light conversion synthesize white light, it is characterized in that adopting silica dioxide granule as fluor matrix, carry out peptization with nitric acid, control pH=2～4, and adding dispersion agent, after the soluble salt of strontium and europium is made into homogeneous solution, atomize, form spherical dry gel particle; This particle carries out the reduction heat decomposition reaction again, can obtain the strontium silicate fluor of europium doped.
2. according to the preparation method of claim 1, it is characterized in that said fluor matrix group becomes Sr
2SiO
4
3. according to the aerosol preparation method of claim 2, it is characterized in that said fluor matrix adopts nano silicon, purity is 99.9-99.99% by percent by weight, and granularity is the 5-40 nanometer.
4. according to the preparation method of claim 3, it is characterized in that said peptization is to use the distilled water dosing, controls silicon-dioxide: water=1: 20～40 by weight.
5. according to the preparation method of claim 1 or 4, it is characterized in that strontium and europium in the said fluor composition adopt water-soluble nitrate or acetate, the purity of salt is percent by weight 〉=99.9%, counts strontium by stoichiometric ratio and atomic molar: europium=1: 0.01～0.05 joins silicon dioxide gel together.
6. according to the preparation method of claim 5, it is characterized in that said dispersion agent is solid polyethylene alcohol or solid alkyl trimethyl class, quantity is the 0.1-5% of colloidal sol gross weight.
7. according to the preparation method of claim 1 or 6, it is characterized in that said solution atomization, is at 110 ℃～250 ℃ of compressed air temperature, dry air amount 100～300m
3/ h atomizes to the doped silicon oxide colloid under streams 1～2L/h, obtains dry gel particle.
8. according to the preparation method of claim 1 or 6, it is characterized in that said particle, reach 1000 ℃～1400 ℃ of temperature, carry out high temperature in time 2-4 hour and burn till at reducing atmosphere.
9. according to the preparation method of claim 7, it is characterized in that said particle, reach 1000 ℃～1400 ℃ of temperature, carry out high temperature in time 2-4 hour and burn till at reducing atmosphere.
10. according to the preparation method of claim 8, it is characterized in that the said reducing atmosphere that burns till can adopt N
2+ H
2, a kind of in gac reduction, decomposed ammonia body or the coal gas.
11., it is characterized in that the said reducing atmosphere that burns till can adopt N according to the preparation method of claim 9
2+ H
2, a kind of in gac reduction, decomposed ammonia body or the coal gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101222537A CN100339460C (en) | 2005-12-09 | 2005-12-09 | Preparation method of silicate luminous body for converting blue light to white light |
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|---|---|---|---|
| CNB2005101222537A CN100339460C (en) | 2005-12-09 | 2005-12-09 | Preparation method of silicate luminous body for converting blue light to white light |
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| CN1786108A CN1786108A (en) | 2006-06-14 |
| CN100339460C true CN100339460C (en) | 2007-09-26 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103013502A (en) * | 2012-12-03 | 2013-04-03 | 合肥工业大学 | Silicate-based fluorescent material and synthetic method thereof |
Families Citing this family (5)
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|---|---|---|---|---|
| CN101892054B (en) * | 2010-07-30 | 2012-11-07 | 陕西科技大学 | Preparation method of white emitting fluorescent powder for LED |
| CN101892049B (en) * | 2010-07-30 | 2012-11-07 | 陕西科技大学 | Preparation method of single matrix white light fluorescent powder for white light LED |
| CN101892048B (en) * | 2010-07-30 | 2012-11-07 | 陕西科技大学 | Preparation method of alkaline earth chloride silicate-based white fluorescent powder for white LED |
| CN102408890A (en) * | 2011-11-15 | 2012-04-11 | 杭州广陵科技开发有限公司 | Silicate green fluorescent powder and preparation method thereof |
| CN104371723B (en) * | 2014-11-12 | 2016-09-14 | 河北利福化工科技有限公司 | A kind of white light LEDs preparation method of efficient class ball-type green emitting phosphor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR920001783B1 (en) * | 1988-12-30 | 1992-03-02 | 삼성전관 주식회사 | Stabilization method of luminescent containing alkaline earth metals |
| JPH06251842A (en) * | 1993-02-22 | 1994-09-09 | Iwasaki Electric Co Ltd | Socket for lamp |
| US5639400A (en) * | 1996-05-31 | 1997-06-17 | Eastman Kodak Company | Stabilized storage phosphors and radiographic screens |
-
2005
- 2005-12-09 CN CNB2005101222537A patent/CN100339460C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR920001783B1 (en) * | 1988-12-30 | 1992-03-02 | 삼성전관 주식회사 | Stabilization method of luminescent containing alkaline earth metals |
| JPH06251842A (en) * | 1993-02-22 | 1994-09-09 | Iwasaki Electric Co Ltd | Socket for lamp |
| US5639400A (en) * | 1996-05-31 | 1997-06-17 | Eastman Kodak Company | Stabilized storage phosphors and radiographic screens |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103013502A (en) * | 2012-12-03 | 2013-04-03 | 合肥工业大学 | Silicate-based fluorescent material and synthetic method thereof |
| CN103013502B (en) * | 2012-12-03 | 2014-10-08 | 合肥工业大学 | Silicate-based fluorescent material and synthetic method thereof |
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| CN1786108A (en) | 2006-06-14 |
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