CN101591535B - Method for preparing alkaline-earth silicate fluorescent powder activated by rare earth elements - Google Patents
Method for preparing alkaline-earth silicate fluorescent powder activated by rare earth elements Download PDFInfo
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- CN101591535B CN101591535B CN200910023107A CN200910023107A CN101591535B CN 101591535 B CN101591535 B CN 101591535B CN 200910023107 A CN200910023107 A CN 200910023107A CN 200910023107 A CN200910023107 A CN 200910023107A CN 101591535 B CN101591535 B CN 101591535B
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000000843 powder Substances 0.000 title claims abstract description 20
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title abstract description 14
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- 229910052788 barium Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 3
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 3
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 3
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 3
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 40
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 23
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 22
- -1 polyoxyethylene Polymers 0.000 claims description 22
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 20
- 239000000084 colloidal system Substances 0.000 claims description 20
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 20
- 238000005303 weighing Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000005245 sintering Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 101100400378 Mus musculus Marveld2 gene Proteins 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000007669 thermal treatment Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 36
- 238000009826 distribution Methods 0.000 abstract description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract description 10
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 238000005538 encapsulation Methods 0.000 abstract 1
- 239000012456 homogeneous solution Substances 0.000 abstract 1
- 238000000643 oven drying Methods 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 64
- 239000012071 phase Substances 0.000 description 50
- 239000002245 particle Substances 0.000 description 12
- 238000003980 solgel method Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000009841 combustion method Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000935 solvent evaporation Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000003407 synthetizing effect Effects 0.000 description 1
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Abstract
The invention discloses a method for preparing alkaline-earth silicate fluorescent powder activated by rare earth elements. The chemical expression formula of the alkaline-earth silicate fluorescent powder is M2-xSiO4:xRe, wherein M is any one or combination of Ca, Mg, Zn, Sr and Ba; Re is one or combination of Ce, Tb, Eu, Dy and Sm; and x is less than or equal to 0.4. The method comprises the following steps: weighting soluble salt of the elements according to stoichiometric proportion; introducing Si element by tetraethoxy silane (TEOS), and preparing various compositions into homogeneous solution; and introducing a microwave oven drying method in a gel preparing process to prepare an alkaline-earth silicate fluorescent material. The method disclosed by the invention has low energy consumption and short cycle; and the prepared product has good dispersibility, small grain diameter and concentrated granularity distribution, is similar to a sphere, optimizes the structural performance of the material, provides convenient condition for LED encapsulation to have even and compact coating, and has active promoting function of improving LED performance.
Description
Technical field
The invention belongs to LED and use the fluorescent material technical field, relate to a kind of preparation method of alkaline-earth silicate fluorescent powder of activated by rare earth elements.
Background technology
The alkaline-earth silicate of activated by rare earth elements is as one type of important luminescent material; Have good chemistry and thermostability; Its excitation spectrum broad; Can be by ultraviolet ray, near-ultraviolet ray, blue-light excitedly present higher luminous efficiency, emmission spectrum covers bigger wavelength region, therefore becomes the important source of LED phosphor material powder.For example, Park etc. has prepared europkium-activated Sr through solid phase method
2SiO
4Produce white light with InGaN chip coupling.
Be accompanied by LED (Light Emitting Diode) continuous advancement in technology and application widely; High-power, the high-efficiency LED that might become lighting source of future generation become the focus of research; This just has higher requirement with the thermostability of fluorescent material to LED, and the alkaline-earth silicate of activated by rare earth elements receives much concern because of its good thermostability.
To have breakthrough aspect high-level efficiency, the great power LED research, obtain a kind ofly to prepare good dispersivity, particle diameter is little, size-grade distribution is concentrated, the method for subsphaeroidal silicate fluorescent powder is most important.At present, the method for preparing fluorescent material mainly comprises: solid phase method, coprecipitation method, combustion method, sol-gel method etc.Generally adopt the solid phase method synthetizing phosphor powder in the industry; Exist reactive component more though method is simple, mixing can not realize enough evenly, the temperature of reaction greater energy consumption is big, product needs ball milling can cause crystal impaired and possibly introduce problem such as impurity effect luminous intensity.Coprecipitation method is different because of the deposition condition of its each component, is difficult to deposition simultaneously, causes easily because of the inhomogeneous luminescent properties that influences of activator doping.Combustion method causes the product synthesis temperature there are differences because of there being different warm areas, is prone to cause the product size distribution inhomogeneous.Sol-gel method has advantages such as energy consumption is low, the products therefrom size distribution is even, particle diameter is little, good dispersivity, but its long production cycle has been limited its popularization in industrial production.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of alkaline-earth silicate fluorescent powder of activated by rare earth elements, on the basis of sol-gel method, improve, shortened preparation cycle.
The technical scheme that technical solution problem of the present invention is taked is:
A kind of preparation method of alkaline-earth silicate fluorescent powder of activated by rare earth elements may further comprise the steps:
According to chemical formula M
2-xSiO
4: xRe confirms the mol ratio of each element of the alkaline-earth silicate fluorescent powder of said activated by rare earth elements, and wherein, M is one or more of Ca, Mg, Zn, Sr or Ba element, and Re is one or more of Ce, Tb, Eu, Dy or Sm element, x≤0.4; Take by weighing that the compound that comprises M, Re is dissolved in deionized water or rare nitric acid obtains homogeneous phase solution; Wherein the concentration of M is 0.01～2mol/l; The concentration of Re is 0.01～0.05mol/l; The concentration that will comprise corresponding Si element again is that the ethanol solution of the tetraethoxy of 0.1～2mol/l splashes into, and fully stirs and obtains homogeneous phase solution A;
Taking by weighing Hydrocerol A and polyoxyethylene glycol, to be dissolved in volume(tric)fraction altogether be 25%～85% ethanolic soln, and the concentration of Hydrocerol A is 0.1～2mol/l, and being added drop-wise to homogeneous phase solution A behind the thorough mixing and regulating the Ph value is 2～7, mixes to obtain homogeneous phase solution B; The mol ratio of metals ion total amount is 2～5 in said Hydrocerol A and the alkaline-earth silicate, the mol ratio 0.015～0.05 of polyoxyethylene glycol and tetraethoxy;
Under 75～95 ℃ of water bath condition, thermostatically heating 2～3 hours obtains transparent colloid C with homogeneous phase solution B;
Transparent colloid C is moved into microwave oven thermal treatment 1～3 hour, obtain the cotton-shaped xerogel D of brown, the power of said microwave oven is 500～800W;
Cotton-shaped xerogel D more than 1 hour, is obtained the alkaline-earth silicate fluorescent powder of activated by rare earth elements at 900～1100 ℃ of sintering.
The sintering of said cotton-shaped xerogel D is sintering under reduction or air atmosphere as required.
Compared with prior art, the present invention has following beneficial technical effects:
1, the present invention passes through sol-gel method; In conjunction with the dry method for preparing gel of microwave oven; Shortened the production cycle of fluorescent material: microwave heating is a kind of material inside that is deep into, heating means from inside to outside, it have rate of heating fast, be quick on the draw, no thermograde existence in the homogeneous heating, microwave heating field, thermo-efficiency advantages of higher; These characteristics can make that the time spent significantly reduces in preparing gel and the drying process, have shortened the cycle of fluorescent material preparation; Solved in traditional sol-gel method preparing gel and the drying process,, thereby avoided reunion and the be full of cracks in the gel drying process, precursor is more disperseed because of the non-uniform capillary pressure that produces in the surface stress that produces and the gel is crossed slowly in solvent evaporation.
2, suitability of the present invention is strong, can be used for preparing multiple activated by rare earth elements alkaline-earth silicate fluorescent powder, and the raw material that is adopted is simple and easy to, and fabrication cycle is short, and products obtained therefrom has broad application prospects.
3, adopt the activated by rare earth elements alkaline-earth silicate fluorescent powder M of the method for the invention preparation
2-xSiO
4: the xRe good dispersivity, particle diameter is little, size-grade distribution is concentrated, subsphaeroidal, in the LED packaging process, be easy to obtain the fluorescent coating of even compact, help the raising of great power LED luminous efficiency.
Description of drawings
Fig. 1 is the Sr of the present invention's preparation
1.92SiO
4: the XRD of 0.08Ce fluorescent material (X-ray diffraction) figure, wherein X-coordinate is the X ray input angle, ordinate zou is the relative intensity of diffraction peak;
Fig. 2 is the Sr of the present invention's preparation
1.92SiO
4: the SEM of 0.08Ce fluorescent material (sem) figure;
Fig. 3 is the Ca of the present invention's preparation
1.94SiO
4: the exciting light spectrogram of 0.06Eu fluorescent material, wherein X-coordinate is an excitation wavelength range, and unit is nanometer (nm), and ordinate zou is that this material is in the ultraviolet ray excited relative intensity of absorption peak down of different wave length;
Fig. 4 is the Ca of the present invention's preparation
1.94SiO
4: the emmission spectrum figure of 0.06Eu fluorescent material, wherein X-coordinate is that emmission spectrum wavelength region unit is nanometer (nm), ordinate zou is that this material is in the ultraviolet ray excited relative intensity of emission peak down of 365nm.
Embodiment
Do detailed description in the face of the present invention down, said is to explanation of the present invention rather than qualification.
The present invention combines the dry method for preparing gel of microwave oven through sol-gel method, has shortened the production cycle of fluorescent material: make that the time spent significantly reduces in preparing gel and the drying process, shortened the cycle that fluorescent material prepares; Solved in traditional sol-gel method preparing gel and the drying process,, thereby avoided reunion and the be full of cracks in the gel drying process because of the non-uniform capillary pressure that produces in the surface stress that produces and the gel is crossed slowly in solvent evaporation.
The activated by rare earth elements alkaline-earth silicate fluorescent powder good dispersivity of the present invention preparation, particle diameter is little, size-grade distribution is concentrated, subsphaeroidal.Can know that like Fig. 1 the gained sample is the orthosilicate crystalline structure, the entering of a small amount of REE does not have influence on whole crystalline network; The Sr of the present invention's preparation as shown in Figure 2
1.92SiO
4: the SEM of 0.08Ce fluorescent material (sem) figure; Show that like Fig. 3, Fig. 4 experiment gained fluorescent material sample is fit to LED ultraviolet chip and excites, the strong visible light of emission is the phosphor material powder of a kind of LED of being applicable to.
Embodiment 1:Sr
1.92SiO
4: the preparation of 0.08Ce fluorescent material
Take by weighing Sr (NO
3)
26.095g, Ce (NO
3)
36H
2O 0.521g is dissolved in the 50ml deionized water, obtains homogeneous phase solution through stirring; Measure again and splash into above-mentioned homogeneous phase solution after tetraethoxy (TEOS) 7.386ml is dissolved in the 20ml absolute ethyl alcohol, fully stir and obtain homogeneous phase solution A;
Take by weighing Hydrocerol A (mol ratio of Hydrocerol A and Sr is 2.5: 1) and polyoxyethylene glycol HO-(CH
2CH
2O)
n-H (molecular weight=6000; A.R.; Polyoxyethylene glycol and tetraethoxy mol ratio be 0.015: 1) be dissolved in 40ml aqueous ethanolic solution (volume(tric)fraction is 25%) altogether, be added drop-wise to homogeneous phase solution A behind the thorough mixing and regulate the Ph value and equal 5, fully stir and it mixed obtain homogeneous phase solution B;
Homogeneous phase solution B is inserted 75 ℃ of heating of constant temperature in the water-bath, obtain transparent colloid C after 3 hours;
Transparent colloid C is moved in the microwave oven dry, microwave power is made as 800W, obtains the cotton-shaped xerogel D of brown in 1 hour;
With at first 500 ℃ of pre-burnings 0.5 hour of xerogel D, 900 ℃ of sintering 3 hours in reducing atmosphere more promptly obtain good dispersivity, particle diameter is little, size-grade distribution is concentrated, subglobose Sr
1.92SiO
4: 0.08Ce fluorescent material.
Embodiment 2:Ca
1.88Mg
0.06SiO
4: the preparation of 0.06Eu fluorescent material
Take by weighing Ca (NO
3)
24.627g, Mg (NO
3)
26H
2O 0.231g, Eu (NO
3)
36H
2O 0.402g is dissolved in the 50ml deionized water, obtains homogeneous phase solution through stirring; Measure tetraethoxy (TEOS) 7.386ml again and be dissolved in the 50ml absolute ethyl alcohol and splash into above-mentioned homogeneous phase solution, fully stir and obtain homogeneous phase solution A;
Take by weighing Hydrocerol A (mol ratio of Hydrocerol A and Ca and Mg is 4: 1) and polyoxyethylene glycol HO-(CH
2CH
2O)
n-H (molecular weight=6000; A.R.; The mol ratio of polyoxyethylene glycol and tetraethoxy is 0.02: 1) be dissolved in 200ml aqueous ethanolic solution (volume(tric)fraction is 35%) altogether, be added drop-wise to homogeneous phase solution A behind the thorough mixing and regulate the Ph value and equal 4, fully stir and it is mixed obtain homogeneous phase solution B;
Homogeneous phase solution B is inserted 90 ℃ of heating of constant temperature in the water-bath, obtain transparent colloid C after 2 hours;
Transparent colloid C is moved in the microwave oven dry, microwave power is made as 600W, obtains the cotton-shaped xerogel D of brown in 1.5 hours;
With at first 500 ℃ of pre-burnings 0.5 hour of xerogel D, 1100 ℃ of sintering 1 hour in reducing atmosphere again obtain good dispersivity, particle diameter is little, size-grade distribution is concentrated, subglobose Ca
1.88Mg
0.06SiO
4: 0.06Eu fluorescent material.
Embodiment 3:Ca
1.94SiO
4: the preparation of 0.06Eu fluorescent material
Take by weighing Ca (NO
3)
24.775g, Eu (NO
3)
36H
2O 0.402g is dissolved in the 100ml ionized water, obtains homogeneous phase solution through stirring; Measure again and splash into above-mentioned homogeneous phase solution after tetraethoxy (TEOS) 7.386ml is dissolved in the 30ml absolute ethyl alcohol, fully stir and obtain homogeneous phase solution A;
Take by weighing Hydrocerol A (mol ratio of Hydrocerol A and Ca is 3: 1) and polyoxyethylene glycol HO-(CH
2CH
2O)
n-H (molecular weight=6000; A.R.; The mol ratio of polyoxyethylene glycol and tetraethoxy is 0.03: 1) be dissolved in 250ml aqueous ethanolic solution (volume(tric)fraction is 50%) altogether, be added drop-wise to homogeneous phase solution A behind the thorough mixing and regulate the Ph value and equal 7, fully stir and it is mixed obtain homogeneous phase solution B;
Homogeneous phase solution B is inserted 85 ℃ of heating of constant temperature in the water-bath, transparent colloid C after 2.5 hours;
Transparent colloid C is moved in the microwave oven dry, microwave power is made as 700W, obtains the cotton-shaped xerogel D of brown in 1.5 hours;
With above-mentioned xerogel D1100 ℃ sintering 2 hours, obtain good dispersivity, particle diameter is little, size-grade distribution is concentrated, subglobose Ca
1.94SiO
4: 0.06Eu fluorescent material.
Embodiment 4:Sr
1.94SiO
4: Ce
0.048, Tb
0.012The preparation of fluorescent material
Take by weighing Sr (NO
3)
26.158g, Ce (NO
3)
36H
2O 0.313g is dissolved in the 50ml deionized water and forms homogeneous phase solution, Tb
4O
7Be added drop-wise to the above-mentioned aqueous solution behind rare nitric acid and fully stir and obtain homogeneous phase solution 60ml 0.135g be dissolved in, measure tetraethoxy (TEOS) 7.386ml again and be dissolved in the 80ml absolute ethyl alcohol and splash into above-mentioned homogeneous phase solution, fully stir and obtain homogeneous phase solution A;
Take by weighing Hydrocerol A (mol ratio of Hydrocerol A and Sr is 5: 1) and polyoxyethylene glycol HO-(CH
2CH
2O)
n-H (molecular weight=6000; A.R.; The mol ratio of polyoxyethylene glycol and tetraethoxy is 0.045: 1) be dissolved in 200ml aqueous ethanolic solution (volume(tric)fraction is 65%) altogether, be added drop-wise to homogeneous phase solution A behind the thorough mixing and regulate the Ph value and equal 7, fully stir and it is mixed obtain homogeneous phase solution B;
Homogeneous phase solution B is inserted 95 ℃ of heating of constant temperature in the water-bath, obtain transparent colloid C after 2 hours;
Transparent colloid C is moved in the microwave oven dry, microwave power is made as 800W, obtains the cotton-shaped xerogel D of brown in 1.5 hours;
With at first 500 ℃ of pre-burnings 0.5 hour of xerogel D, 1100 ℃ of sintering 2 hours in reducing atmosphere more promptly obtain good dispersivity, particle diameter is little, size-grade distribution is concentrated, subglobose Sr
1.94SiO
4: Ce
0.048, Tb
0.012Fluorescent material.
Embodiment 5:Ba
1.94SiO
4: the preparation of 0.06Eu fluorescent material
Take by weighing Ba (NO
3)
27.605g, Eu (NO
3)
36H
2O 0.402g is dissolved in the 200ml deionized water, obtains homogeneous phase solution through stirring, and measures and splashes into above-mentioned solution after tetraethoxy (TEOS) 7.386ml is dissolved in the 40ml absolute ethyl alcohol, fully stirs and obtains homogeneous phase solution A;
Take by weighing an amount of Hydrocerol A (mol ratio of Hydrocerol A and Ba is 3: 1) and polyoxyethylene glycol HO-(CH
2CH
2O)
n-H (molecular weight=6000; A.R.; The mol ratio of polyoxyethylene glycol and tetraethoxy is 0.1: 1) be dissolved in 50ml aqueous ethanolic solution (volume(tric)fraction is 85%) altogether, be added drop-wise to homogeneous phase solution A behind the thorough mixing and regulate the Ph value and equal 5, fully stir and it is mixed obtain homogeneous phase solution B;
Homogeneous phase solution B is inserted 90 ℃ of heating of constant temperature in the water-bath, transparent colloid C after 2.5 hours;
Above-mentioned transparent colloid is moved in the microwave oven dry, microwave power is made as 500W, obtains the cotton-shaped xerogel D of brown in 3 hours;
With at first 500 ℃ of pre-burnings 0.5 hour of above-mentioned xerogel D, 1100 ℃ of sintering 2 hours in reducing atmosphere more promptly obtain good dispersivity, particle diameter is little, size-grade distribution is concentrated, subglobose Ba
1.94SiO
4: 0.06Eu.
Embodiment 6:Ca
1.2Mg
0.4SiO
4: the preparation of 0.4Dy fluorescent material
Take by weighing Ca (NO
3)
22.954g, Mg (NO
3)
36H
2O 1.538g, Dy (NO
3)
36H
2O 1.934g is dissolved in the 50ml deionized water, obtains homogeneous phase solution through stirring, and measures and splashes into above-mentioned solution after tetraethoxy (TEOS) 7.386ml is dissolved in the 20ml absolute ethyl alcohol, fully stirs and obtains homogeneous phase solution A;
Take by weighing an amount of Hydrocerol A (mol ratio of Hydrocerol A and Ca and Mg is 4: 1) and polyoxyethylene glycol HO-(CH
2CH
2O)
n-H (molecular weight=6000; A.R.; The mol ratio of polyoxyethylene glycol and tetraethoxy is 0.025: 1) be dissolved in 80ml aqueous ethanolic solution (volume(tric)fraction is 30%) altogether, be added drop-wise to A solution behind the thorough mixing and regulate the Ph value and equal 5, fully mix and obtain homogeneous phase solution B;
Homogeneous phase solution B is inserted 85 ℃ of heating of constant temperature in the water-bath, transparent colloid C after 2.5 hours;
Transparent colloid C is moved in the microwave oven dry, microwave power is made as 800W, obtains the cotton-shaped xerogel D of brown in 1.5 hours;
To go up xerogel D1000 ℃ sintering 2 hours, promptly obtain good dispersivity, particle diameter is little, size-grade distribution is concentrated, subglobose Ca
1.2Mg
0.4SiO
4: 0.4Dy fluorescent material.
Embodiment 7:Ba
1.8Zn
0.1SiO
4: the preparation of 0.1Sm fluorescent material
Take by weighing Ba (NO
3)
27.056g, Zn (NO
3)
36H
2O 0.446g, Sm (NO
3)
36H
2O 0.667g is dissolved in the 50ml deionized water, obtains homogeneous phase solution through stirring, and measures and splashes into above-mentioned solution after tetraethoxy (TEOS) 7.386ml is dissolved in the 20ml absolute ethyl alcohol, fully stirs and obtains homogeneous phase solution A;
Take by weighing an amount of Hydrocerol A (mol ratio of Hydrocerol A and Zn and Ba is 4: 1) and polyoxyethylene glycol HO-(CH
2CH
2O)
n-H (molecular weight=6000; A.R.; The mol ratio of polyoxyethylene glycol and tetraethoxy is 0.05: 1) be dissolved in 50ml aqueous ethanolic solution (volume(tric)fraction is 45%) altogether, be added drop-wise to homogeneous phase solution A behind the thorough mixing and regulate the Ph value and equal 5, fully mix and obtain homogeneous phase solution B;
Homogeneous phase solution B is inserted 85 ℃ of heating of constant temperature in the water-bath, transparent colloid C after 2.5 hours;
Transparent colloid C is moved in the microwave oven dry, microwave power is made as 800W, obtains the cotton-shaped xerogel D of brown in 1.5 hours;
With above-mentioned xerogel D1000 ℃ sintering 2 hours, promptly obtain good dispersivity, particle diameter is little, size-grade distribution is concentrated, subglobose Ba
1.8Zn
0.1SiO
4: 0.1Sm fluorescent material.
Embodiment 8:Sr
1.92SiO
4: the preparation of 0.08Ce fluorescent material
Take by weighing Sr (NO
3)
26.095g, Ce (NO
3)
36H
2O 0.521g is dissolved in the 30ml deionized water, obtains homogeneous phase solution through stirring; Measure again and splash into above-mentioned homogeneous phase solution after tetraethoxy (TEOS) 7.386ml is dissolved in the 50ml absolute ethyl alcohol, fully stir and obtain homogeneous phase solution A;
Take by weighing Hydrocerol A (mol ratio of Hydrocerol A and Sr is 2.5: 1) and polyoxyethylene glycol HO-(CH
2CH
2O)
n-H (molecular weight=6000; A.R.; Polyoxyethylene glycol and tetraethoxy mol ratio be 0.015: 1) be dissolved in 50ml aqueous ethanolic solution (volume(tric)fraction is 65%) altogether, be added drop-wise to homogeneous phase solution A behind the thorough mixing and regulate the Ph value and equal 5, fully stir and it mixed obtain homogeneous phase solution B;
Homogeneous phase solution B is inserted 75 ℃ of heating of constant temperature in the water-bath, obtain transparent colloid C after 3 hours;
Transparent colloid C is moved in the microwave oven dry, microwave power is made as 500W, obtains the cotton-shaped xerogel D of brown in 3 hours;
With at first 500 ℃ of pre-burnings 0.5 hour of xerogel D, 900 ℃ of sintering 3 hours in reducing atmosphere more promptly obtain good dispersivity, particle diameter is little, size-grade distribution is concentrated, subglobose Sr
1.92SiO
4: 0.08Ce fluorescent material.
Claims (2)
1. the preparation method of the alkaline-earth silicate fluorescent powder of an activated by rare earth elements is characterized in that, may further comprise the steps:
According to chemical formula M
2-xSiO
4: xRe confirms the mol ratio of each element of the alkaline-earth silicate fluorescent powder of said activated by rare earth elements, and wherein, M is one or more of Ca, Mg, Zn, Sr or Ba element, and Re is one or more of Ce, Tb, Eu, Dy or Sm element, x≤0.4; Take by weighing that the compound that comprises M, Re is dissolved in deionized water or rare nitric acid obtains homogeneous phase solution; Wherein the concentration of M is 0.01～2mol/l; The concentration of Re is 0.01～0.05mol/l; The concentration that will comprise corresponding Si element again is that the ethanol solution of the tetraethoxy of 0.1～2mol/l splashes into, and fully stirs and obtains homogeneous phase solution A;
Taking by weighing Hydrocerol A and polyoxyethylene glycol, to be dissolved in volume(tric)fraction altogether be 25%～85% ethanolic soln, and the concentration of Hydrocerol A is 0.1～2mol/l, and being added drop-wise to homogeneous phase solution A behind the thorough mixing and regulating the pH value is 2～7, mixes to obtain homogeneous phase solution B; The mol ratio of metals ion total amount is 2～5 in said Hydrocerol A and the alkaline-earth silicate, the mol ratio 0.015～0.05 of polyoxyethylene glycol and tetraethoxy;
Under 75～95 ℃ of water bath condition, thermostatically heating 2～3 hours obtains transparent colloid C with homogeneous phase solution B;
Transparent colloid C is moved into microwave oven thermal treatment 1～3 hour, obtain the cotton-shaped xerogel D of brown, the power of said microwave oven is 500～800W;
Cotton-shaped xerogel D more than 1 hour, is obtained the alkaline-earth silicate fluorescent powder of activated by rare earth elements at 900～1100 ℃ of sintering.
2. the preparation method of the alkaline-earth silicate fluorescent powder of activated by rare earth elements as claimed in claim 1 is characterized in that, the sintering of cotton-shaped xerogel D is sintering under reducing atmosphere.
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