CN100503769C - Method for preparing efficient fine-particle blue fluorescent powder - Google Patents
Method for preparing efficient fine-particle blue fluorescent powder Download PDFInfo
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- CN100503769C CN100503769C CNB2003101112595A CN200310111259A CN100503769C CN 100503769 C CN100503769 C CN 100503769C CN B2003101112595 A CNB2003101112595 A CN B2003101112595A CN 200310111259 A CN200310111259 A CN 200310111259A CN 100503769 C CN100503769 C CN 100503769C
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- 239000000843 powder Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000010419 fine particle Substances 0.000 title description 2
- 239000000463 material Substances 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 24
- 238000005303 weighing Methods 0.000 claims description 24
- 239000003352 sequestering agent Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 15
- 239000012153 distilled water Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- -1 aluminum ions Chemical class 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 229910052693 Europium Inorganic materials 0.000 claims description 4
- 229910001422 barium ion Inorganic materials 0.000 claims description 4
- 159000000009 barium salts Chemical class 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 159000000003 magnesium salts Chemical class 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical group [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims 1
- 229910001626 barium chloride Inorganic materials 0.000 claims 1
- 229940045511 barium chloride Drugs 0.000 claims 1
- 229910001629 magnesium chloride Inorganic materials 0.000 claims 1
- 238000009841 combustion method Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 2
- 239000000047 product Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003746 solid phase reaction Methods 0.000 description 4
- 238000010671 solid-state reaction Methods 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012190 activator Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- ZQBKQZMRKNZHLL-UHFFFAOYSA-N mercury neon Chemical compound [Ne].[Hg] ZQBKQZMRKNZHLL-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
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Abstract
The invention relates to a kind of preparation method of approred beaded blue cast powder. The combustion method of sol-gel is adopted, which composing supersonic wave art. the caliber of end product transits controlling initial concentration, forming time, initial concentration of burning, calcining heat, cooling velocity, and other preparation art. the process conditions make sure that the size of the end product is 300mm and the cast powder with higher capability of irradiance. Besides, gather the supersonic wave artistic, the base material can be mixed uniformly and the short grained cast powder has higher quality and exact small gauge. Thus, a lot of manufacturing procedure can be canceled, for example, the rubbing to convergency the size of the cast powder will be canceled because the rubbing would destroy the cryst framework of the powder and depress the luminous efficiency.
Description
Technical field
The present invention relates to the luminescent material technical field, promptly be used for the required fluor of purposes such as color plasma display panel (PDP), compact type energy-saving lamp, no mercury neon light, the novel background light source of liquid-crystal display, prepare the method for blue-fluorescence powder especially.
Technical background
Recent years, the development of a kind of novel flat-plate indicating meter-color plasma flat-panel monitor (PDP) rapidly, this PDP indicating meter has large size, advantages such as in light weight and panelized, it utilizes noble gas discharge and luminous.In the PDP device, the vacuum-ultraviolet light (VUV) that produces by glow discharge excites the red, green, blue three primary colors fluorescent powder luminous, thereby realizes colored the demonstration.The glow discharge of Xe-Ne mixed gas produces wavelength at the VUV of 147～190nm light, 147nm light luminous intensity height wherein, and energy is big, so PDP mainly uses it as excitation light source, excited fluophor is luminous.Some VUV light also can excited fluophor in addition.At present,, still there is the manufacturing cost height, problem such as luminous efficiency is low though the PDP indicating meter progressively comes into the market.Due to the luminous efficiency that the major reason that luminous efficiency is low is exactly the conventional blue fluorescent powder is low, therefore, improving the luminous efficiency of blue-fluorescence powder, is a problem that presses for solution.
In order to obtain the fluorescent material of better performance and high-luminous-efficiency, flat display apparatus is PDPs for example, Field Emission Display (FED) and electroluminescent (EL) plate need have the fluor of fine particle (0.1-2 micron), and it is more urgent to be coated with this demand of screen technology for PDP.Small-particle also can provide higher tap density and binder content still less.Therefore be convenient to make the enforcement of screen novel process with the small-particle blue emitting phophor, help making the development of ultra-thin display screen technology.
BaMgAl
10O
17: Eu
2+(BAM) can use as PDP blue-fluorescence powder.People are to its preparation method, luminescence mechanism, and decay mechanisms has been carried out many researchs.At present, the usual method for preparing this fluorescent powder is high temperature solid state reaction (SSR) method, promptly mixes BaCO
3, Mg (OH)
2, Al
2O
3With Eu
2O
3And fusing assistant is at H
2/ N
2(H
2Be 5%, N
2Be 95%) in the reducing atmosphere 1600 ℃ of calcinations make, (referring to Shuxiu Zhang, Masataka Kokubu etc.:A Study on theChromaticity shifts of blue phosphors for color plasma displays.Journal of the SID 10/1,2002,25～29) adopt the mode of ball milling to reduce granularity.The blue-fluorescence powder of this method preparation exists that sintering temperature is too high, particle is inhomogeneous, rare earth disperses inhomogeneous and reduces granularity by ball milling method and can reduce shortcomings such as luminescent properties.
Summary of the invention
Technical problem to be solved by this invention is: a kind of method for preparing efficient small-particle blue-fluorescence powder is provided, this method temperature of reaction is significantly less than the temperature of reaction of SSR method, prepare efficient small-particle blue-fluorescence powder with this method, particle is tiny evenly, and its luminescent properties is good.
The method steps that the present invention solves the problems of the technologies described above the technical scheme that is adopted is:
(1) take by weighing soluble barium salt, solubility magnesium salts, aluminum soluble salt and put into container respectively, the ratio of barium ion, magnesium ion, aluminum ions mole number is 1: 0.8-1.6: 9-11; Add distilled water respectively in container, be mixed in the container after the dissolving fully, stirring makes it to mix, and gets solution A;
(2) ratio according to barium ion and the mole number of europium ion is 100: the ratio of 5-20 takes by weighing europium sesquioxide, adds HCl, and heating makes it to dissolve fully, solution B;
(3) solution B is added in the solution A, stirs, it is mixed, get solution C;
(4) preparation sequestrant, the preparation method of sequestrant is: take by weighing ethylenediamine tetraacetic acid (EDTA), the ratio of total mole number of the mole number of ethylenediamine tetraacetic acid (EDTA) and barium, magnesium, aluminium, europium ion is: 1.5-3: 1; Add distilled water and ammoniacal liquor, the ratio of the mole number of distilled water and ethylenediamine tetraacetic acid (EDTA) is 25:1, and the ratio of the mole number of distilled water and ammoniacal liquor is 3.5-5:1;
(5) solution C, sequestrant were disperseed 15-30 minute in ultrasonic wave respectively, sequestrant is joined in the solution C, get solution D;
(6) measure the chelating auxiliary agent, and join in the solution D, stir, uniform mixing gets solution E; Described chelating auxiliary agent is an ethylene glycol, and volume is the 5%-15% of solution D volume, and stirs, and regulates the pH value to 7 of mixing solutions in the whipping process with ammoniacal liquor;
(7) solution E is put into 60 ℃-80 ℃ water-bath, the pH value with ammoniacal liquor control solution E makes it to be stabilized between the 6-8; When forming flaxen colloidal sol, from water-bath, take out cooling;
(8) colloidal sol with gained moves in the crucible, puts into the retort furnace that is warming up to 500 ℃-700 ℃, treat all burnt after, furnace temperature is risen to 800 ℃-1000 ℃, be incubated 2-6 hour;
(9) crucible is put in the hydrogen nitrogen protection stove and heated, when temperature rises to 300 ℃-700 ℃, feed hydrogen, nitrogen shielding gas, the ratio of the volume of hydrogen, nitrogen is 1-2:18-19, be incubated calcination 3-6 hour down at 900-1300 ℃, cooling makes fluorescent material product in early stage;
(10) the fluorescent material product places the ultrasonic wave dispersion treatment in earlier stage; The ultrasonic dispersing treatment process is: will early stage the fluorescent material product, at first under whipped state, in volume ratio is 30%～70% HCl solution, soaked 20～100 minutes, placed the ultrasonic wave dispersion treatment then 60～120 minutes;
(11) with the fluorescent material product drying after the ultra-sonic dispersion processing, can obtain required efficient small-particle blue colour fluorescent powder, its empirical formula is:
X=9-11 wherein; Y=0.05-0.2, its particle size is less than 300nm;
The present invention is directed to the shortcoming that the SSR method exists, adopt the sol-gel combustion method, colloidal sol is the dispersion of colloidal particles in liquid, and the gravity that acts on the particle is ignored.Colloidal sol forms the peaceful all length of the crosslinked rigidity network with submicron pore rapidly at the gel of the polymer chain of micron number magnitude under the high temperature.Gel is very fast burning under the heating condition that is rapidly heated, and the moment high temperature that burning produces provides synthetic needed temperature, calcines needed temperature thereby reduced product.Owing to all raw materials in the synthesis system mix, can obtain the homogeneity of height again on molecular level.Impurity (activator) introducing of being undertaken by solution is direct, easy and is effective.The moment high temperature that gel combustion produces can guarantee the synthetic fully of base matter, and simultaneously, the gas that burning produces can prevent effectively also that particulate from reuniting and grow up.
The inventive method adopts the sol-gel combustion method, and synthetic in conjunction with using ultrasonic technology, the particle size size of final product is finished by the serial preparation process conditions such as initial concentration, formation time, burning starting temperature, calcining temperature and speed of cooling of controlling initial colloidal sol.Processing condition have guaranteed its particle size less than 300nm, have the formation that low particle size shows the fluorescent powder final product that improves luminescent properties.The introducing of ultrasonic technology in addition, the purity and the small size of the uniform mixing and the short grained formation fluorescent powder grain of raw material have further been guaranteed, can cancel many post-treatment operations, as reduce the crystalline structure that the required grinding of fluor size/mill etc. can destroy fluor, reduce the luminous efficiency operation.
Description of drawings
Fig. 1 is the TEM examining report of preparation sample
Fig. 2 detects collection of illustrative plates for the preparation sample at Japanese RIGAKU D/Max-3B powder crystal diffractometer
Fig. 3 is for exciting the luminescent properties graphic representation of measuring behind the preparation sample 4 to prepare the spectral radiation curves of sample for detection in F-4500 type spectrophotofluorometer with 147nm in PDP fluorescent material optical characteristic test system
Specific embodiments
Embodiment 1: accurately weighing 2.4427 restrains BaCl
22H
2O (AR), 2.0330 gram MgCl
26H
2O (AR), 24.1430 gram AlCl
36H
2O (AR) after dissolving fully respectively in beaker, is transferred in another 1000ml beaker, and thorough mixing gets solution A; Take by weighing 0.176 gram Eu in addition
2O
3(99.99%), add 20ml1:1HCl (AR), heating makes it to dissolve fully, gets solution B; Solution B is added in the solution A, stirs, it is mixed, get solution C, ultra-sonic dispersion mixing 15-30 minute; Take by weighing 52.605 gram ethylenediamine tetraacetic acid (EDTA)s (AR), add 100ml distilled water, and then add 30mlNH
3H
2O (AR) stirs, and makes it to dissolve fully, obtains sequestrant, about 15～30 minutes of ultra-sonic dispersion; Sequestrant is joined in the solution C, get solution D; Add about 70ml chelating auxiliary agent ethylene glycol (AR), mixed liquid 10-15 minute, and be 7 with ammoniacal liquor regulator solution pH value, solution E; Solution E inserted constant temperature in 60 ℃～80 ℃ the water-bath, and constantly regulate the pH value, remain on 7.When no longer including moisture evaporation, can obtain flaxen colloidal sol, colloidal sol is taken out cooling from water-bath; Colloidal sol is forwarded in the ceramic crucible, and crucible placed be warmed up to 500 ℃～700 ℃ retort furnace, colloidal sol is converted into gel therein rapidly, and violent burning takes place, after burning is finished, furnace temperature is risen to 800 ℃～1000 ℃ and kept constant temperature 3～6 hours; Products therefrom is forwarded in the corundum crucible, and place hydrogen nitrogen protection stove, when temperature rises to 300 ℃～700 ℃, feed hydrogen nitrogen shielding gas (H
2Volume ratio is about 5%～10%), the insulation calcination is 3～6 hours in the time of 900～1300 ℃, and furnace cooling makes fluorescent material product in early stage.With cooled early stage the fluorescent material product to join the volume ratio that fills 200ml be in the beaker of 30%～70%HCl solution, under whipped state, soaked 20～100 minutes, ultra-sonic dispersion is 60～120 minutes then, filter, dry in 40 ℃～60 ℃ environment, promptly can obtain required efficient small-particle blue-fluorescence powder
(x＝9～11；y＝0.05～0.2)。
The performance table of embodiment 1 preparation sample is as follows:
Embodiment 2: accurately weighing 2.4427 restrains BaCl
22H
2O (AR), 2.0330 gram MgCl
26H
2O (AR), 26.5573 gram AlCl
36H
2O (AR) after dissolving fully respectively in beaker, is transferred in another 1000ml beaker, and thorough mixing gets solution A; Take by weighing 0.176 gram Eu in addition
2O
3(99.99%), add 20ml1:1HCl (AR), heating makes it to dissolve fully, gets solution B; Solution B is added in the solution A, stirs, it is mixed, get solution C, ultra-sonic dispersion mixing 15-30 minute; Take by weighing 56.988 gram ethylenediamine tetraacetic acid (EDTA)s (AR), add 100ml distilled water, and then add 35mlNH
3H
2O (AR) stirs, and makes it to dissolve fully, obtains sequestrant,, about 15 minutes of ultra-sonic dispersion joins sequestrant in the solution C, gets solution D; , all the other steps are with embodiment 1.
Embodiment 3: accurately weighing 4.8854 restrains BaCl
22H
2O (AR), 4.0660 gram MgCl
26H
2O (AR), 48.2860 gram AlCl
36H
2O (AR) after dissolving fully respectively in beaker, is transferred in another 2000ml beaker, and thorough mixing gets solution A; Take by weighing 0.352 gram Eu in addition
2O
3(99.99%), add 40ml1:1HCl (AR), heating makes it to dissolve fully, gets solution B; Solution B is added in the solution A, stirs, it is mixed, get solution C, ultra-sonic dispersion mixed 30 minutes; Take by weighing 105.2100 gram ethylenediamine tetraacetic acid (EDTA)s (AR), add 200ml distilled water, and then add 60mlNH
3H
2O stirs, and makes it to dissolve fully, obtains sequestrant, and about 15 minutes of ultra-sonic dispersion joins sequestrant in the solution C, gets solution D; Add about 120ml chelating auxiliary agent ethylene glycol (AR), all the other steps are with embodiment 1.
Embodiment 4: accurately weighing 2.4427 restrains BaCl
22H
2O (AR), 2.0330 gram MgCl
26H
2O (AR), 24.1430 gram AlCl
36H
2O (AR) after dissolving fully respectively in beaker, is transferred in another 1000ml beaker, and thorough mixing gets solution A; Take by weighing 0.2640 gram Eu in addition
2O
3(99.99%), add 30ml1:1HCl (AR), heating makes it to dissolve fully, gets solution B; Solution B is added in the solution A, stirs, it is mixed, get solution C, ultra-sonic dispersion mixed 15 minutes; Take by weighing 70.140 gram ethylenediamine tetraacetic acid (EDTA)s (AR), add 150ml distilled water, and then add 50mlNH
3H
2O stirs, and makes it to dissolve fully, obtains sequestrant, and about 15 minutes of ultra-sonic dispersion joins sequestrant in the solution C, gets solution D; All the other steps are with embodiment 1.
Embodiment 5: accurately weighing 2.4427 restrains BaCl
22H
2O (AR), 1.6264 gram MgCl
26H
2O (AR), 26.5573 gram AlCl
36H
2O (AR) after dissolving fully respectively in beaker, is transferred in another 1000ml beaker, and thorough mixing gets solution A; Take by weighing 0.176 gram Eu in addition
2O
3(99.99%), add 20ml1:1HCl (AR), heating makes it to dissolve fully, gets solution B; Solution B is added in the solution A, stirs, it is mixed, get solution C, ultra-sonic dispersion mixing 15-30 minute; Take by weighing 56.988 gram ethylenediamine tetraacetic acid (EDTA)s (AR), add 100ml distilled water, and then add 35mlNH
3H
2O (AR) stirs, and makes it to dissolve fully, obtains sequestrant,, about 15 minutes of ultra-sonic dispersion joins sequestrant in the solution C, gets solution D; , all the other steps are with embodiment 1.
Embodiment 6: accurately weighing 2.4427 restrains BaCl
22H
2O (AR), 3.2528 gram MgCl
26H
2O (AR), 24.1430 gram AlCl
36H
2O (AR) after dissolving fully respectively in beaker, is transferred in another 1000ml beaker, and thorough mixing gets solution A; Take by weighing 0.176 gram Eu in addition
2O
3(99.99%), add 20ml1:1HCl (AR), heating makes it to dissolve fully, gets solution B; Solution B is added in the solution A, stirs, it is mixed, get solution C, ultra-sonic dispersion mixing 15-30 minute; Take by weighing 56.988 gram ethylenediamine tetraacetic acid (EDTA)s (AR), add 100ml distilled water, and then add 35mlNH
3H
2O (AR) stirs, and makes it to dissolve fully, obtains sequestrant,, about 15 minutes of ultra-sonic dispersion joins sequestrant in the solution C, gets solution D; , all the other steps are with embodiment 1.
Shown in Fig. 1,2,3,4, implement the above resulting fluorescent material product of each embodiment, under VUV and shortwave UV light and electron-beam excitation, launch strong blue light, main emission peak is 450nm.The fluorescent powder grain that this method is prepared is tiny evenly, good dispersion property, time of persistence short, Heat stability is good, its performance meets color plasma display (PDP) fully to the fluorescent material performance demands.
Claims (2)
1, a kind of method for preparing efficient small-particle blue-fluorescence powder, it is characterized in that: its method steps is:
(1) take by weighing soluble barium salt, solubility magnesium salts, aluminum soluble salt and put into container respectively, the ratio of barium ion, magnesium ion, aluminum ions mole number is 1: 0.8-1.6: 9-11; Add distilled water respectively in container, be mixed in the container after the dissolving fully, stirring makes it to mix, and gets solution A;
(2) ratio according to barium ion and the mole number of europium ion is 100: the ratio of 5-20 takes by weighing europium sesquioxide, adds HCl, and heating makes it to dissolve fully, solution B;
(3) solution B is added in the solution A, stirs, it is mixed, get solution C;
(4) preparation sequestrant, the preparation method of sequestrant is: take by weighing ethylenediamine tetraacetic acid (EDTA), the ratio of total mole number of the mole number of ethylenediamine tetraacetic acid (EDTA) and barium, magnesium, aluminium, europium ion is: 1.5-3: 1; Add distilled water and ammoniacal liquor, the ratio of the mole number of distilled water and ethylenediamine tetraacetic acid (EDTA) is 25:1, and the ratio of the mole number of distilled water and ammoniacal liquor is 3.5-5:1;
(5) solution C, sequestrant were disperseed 15-30 minute in ultrasonic wave respectively, sequestrant is joined in the solution C, get solution D;
(6) measure the chelating auxiliary agent, and join in the solution D, stir, uniform mixing gets solution E; Described chelating auxiliary agent is an ethylene glycol, and volume is the 5%-15% of solution D volume, and stirs, and regulates the pH value to 7 of mixing solutions in the whipping process with ammoniacal liquor;
(7) solution E is put into 60 ℃-80 ℃ water-bath, the pH value with ammoniacal liquor control solution E makes it to be stabilized between the 6-8; When forming flaxen colloidal sol, from water-bath, take out cooling;
(8) colloidal sol with gained moves in the crucible, puts into the retort furnace that is warming up to 500 ℃-700 ℃, treat all burnt after, furnace temperature is risen to 800 ℃-1000 ℃, be incubated 2-6 hour;
(9) crucible is put in the hydrogen nitrogen protection stove and heated, when temperature rises to 300 ℃-700 ℃, feed hydrogen, nitrogen shielding gas, the ratio of the volume of hydrogen, nitrogen is 1-2:18-19, be incubated calcination 3-6 hour down at 900-1300 ℃, cooling makes fluorescent material product in early stage;
(10) the fluorescent material product places the ultrasonic wave dispersion treatment in earlier stage; The ultrasonic dispersing treatment process is: will early stage the fluorescent material product, at first under whipped state, in volume ratio is 30%～70% HCl solution, soaked 20～100 minutes, placed the ultrasonic wave dispersion treatment then 60～120 minutes;
(11) with the fluorescent material product drying after the ultra-sonic dispersion processing, can obtain required efficient small-particle blue colour fluorescent powder, its empirical formula is:
X=9-11 wherein; Y=0.05-0.2, its particle size is less than 300nm.
2, preparation method as claimed in claim 1 is characterized in that: described soluble barium salt is a bariumchloride, and the solubility magnesium salts is a magnesium chloride, and aluminum soluble salt is an aluminum chloride.
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Non-Patent Citations (4)
| Title |
|---|
| 溶胶-凝胶法制备BaMgAl10O17:Eu荧光粉的研究. 张世英等.中国陶瓷工业，第10卷第2期. 2003 |
| 溶胶-凝胶法制备BaMgAl10O17:Eu荧光粉的研究. 张世英等.中国陶瓷工业，第10卷第2期. 2003 * |
| 溶胶-凝胶法合成BaMgAl10O17粉末. 张俊英等.硅酸盐学报，第30卷第1期. 2002 |
| 溶胶-凝胶法合成BaMgAl10O17粉末. 张俊英等.硅酸盐学报，第30卷第1期. 2002 * |
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| CN1580178A (en) | 2005-02-16 |
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