CN101182413A - Method for preparing rare earth aluminate matrix fluorescent powder - Google Patents
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Abstract
The preparation method of the aluminate matrix fluorescent powder comprises seven steps of raw material pretreatment, wet mixing, primary high-temperature air synthesis, primary crushing and grading, secondary high-temperature reduction, secondary grading and surface coating, and finally the aluminate fluorescent powder finished product with the surface coated with the MgO film is obtained. The method of the invention fully combines the advantages of a wet chemical method, a solid phase reaction method and a modern jet milling grading technology, improves the reaction activity of the synthetic raw materials by the pretreatment of the synthetic raw materials and a wet mixing process, and simultaneously combines a high-temperature solid phase method and a jet grading technology, can effectively control the central particle size and the distribution of the fluorescent powder, can finally manufacture the fluorescent powder product with high luminous efficiency and fine and concentrated particle size distribution, and has obvious application prospect.
Description
Technical field
The present invention relates to a kind of manufacture method of aluminate substrate fluorescent powder, particularly plasma panel display (PDP) belongs to field of light emitting materials with the manufacture method of fluorescent material and fluorescent powder of luminescent diode.
Background technology
(Plasma Display Panel PDP) is vacuum ultraviolet ray (VUV) excitated fluorescent powder that utilizes the inert mixed gas discharge generation to the chromatic plasma flat-panel monitor, realizes the video picture purpose.PDP is 100～200nm with the excitation wavelength range of fluorescent material, and main excitation band is near 147nm and 172nm.
The composition of the red-green-blue fluorescent material in the most frequently used PDP of being used for field is at present: rouge and powder (Y
2O
3: Eu
3+, (Y, Gd) BO
3: Eu
3+), green powder (ZnSiO
4: Mn
2+, BaAl
12O
19: Mn
2+), blue powder (BaMgAl
10O
17: Eu
2+) these several fluorescent material since its have good illumination efficiency and chemical stability, be widely used in the plasma display field.
The present green powder (Ba of aluminate substrate
1-z, Sr
x, Mg
y) OaAl
2O
3: Mn
z(wherein 0＜x≤1,0＜y≤1.5,0.01＜z≤0.5, a is the integer that is between 1～23) and aluminate substrate blue powder (Ba
1-m, Sr
n, Mg
p) 0bAl
2O
3: Eu
m(wherein 0≤n≤1,0＜p＜2,0.005＜m≤0.2, b is the integer that is between 1～23) is owing in the comprehensive advantage of each side such as luminous efficiency, purity of color and chemical stability, become the first-selection of PDP with fluorescent material.Thereby, be the emphasis that research circle pays close attention at the blue powder of this type of aluminate-base plastome or the development of green powder all the time.
Over the past two years, for the requirement of meeting digitizing on the horizon and high definition to show, the resolving power of PDP display screen by original VGA level (852 * 480) gradually to XGA or WXGA level (1280 * 720) even higher grade development, adapt therewith, blocking spacing and will further reduce in the PDP panel, thus the particle diameter index of fluorescent material is had higher requirement, promptly require fluorescent material not only to have outside the higher luminous efficiency, also must possess more tiny medium particle diameter and more concentrated particle size distribution characteristics.Just because of this, have fine grain size and high luminescent properties concurrently is the technical bottleneck of the high-quality PDP fluorescent material of restriction always, be considered to weigh a key index of PDP fluorescent material quality, thereby how obtain out the core technology that manufacturing technology that the light efficiency height has tiny particle diameter and narrow distribution thereof simultaneously just becomes PDP fluorescent material.
At present, external commercial PDP adopts high-temperature solid phase reaction method to prepare with aluminate substrate fluorescent powder still more.It is simple that high temperature solid-state method has technical process, advantages such as product with stable quality.But in building-up process in order to guarantee that thing is synthesized mutually at a lower temperature, generally need be by adding fusing assistant to achieve the above object.Comparatively seriously put sintering but can cause powder to produce thus, between the particle adhesion serious, must diameter of particle be reduced to satisfy actual service requirements by mechanical disintegration.Therefore, develop luminous efficiency aluminate substrate fluorescent powder high and that have tiny diameter of particle concurrently is the emphasis that the researchist pays close attention to always.
In order to reach this purpose, people carry out a large amount of developments and trial again in succession on wet chemistry methods such as coprecipitation method, so-gel, spray pyrolysis and combustion method, although also obtained progress and achievement in various degree, but up to now, because it is not enough that these wet chemistry methods exist at different aspects such as technology controlling and process, quality guarantee, costs, still is difficult to be applied to actual production.
Summary of the invention
What the present invention will solve is exactly the problem that above-mentioned prior art exists, and a kind of manufacture method of aluminate substrate fluorescent powder is provided, and to obtain the PDP aluminate fluorescent powder of high brightness, fine grain size, satisfies following high definition PDP display body requirements at the higher level.
The present invention reasonably carries out combination with solid phase method and wet chemistry method advantage separately, the fluorescent material of preparation not only has higher luminous efficiency, also can guarantee simultaneously under the prerequisite that fluorescent powder grain degree of crystallinity do not suffer a loss, obtain more tiny particle diameter and narrower Tile Width, thereby can satisfy actual service requirements better.
Aluminate substrate fluorescent powder of the present invention is the green powder (Ba of aluminate substrate
1-z, Sr
x, Mg
y) OaAl
2O
3: Mn
z(wherein 0＜x≤1,0＜y≤1.5,0.01＜z≤0.5, a is the integer that is between 1～23) and aluminate substrate blue powder (Ba
1-m, Sr
n, Mg
p) ObAl
2O
3: Eu
m(wherein 0≤n≤1,0＜p＜2,0.005≤m≤0.2, b is the integer that is between 1～23), manufacture method may further comprise the steps:
(1) raw materials pretreatment
Be distributed in the acid solution that volumetric molar concentration is 0.1M～2.0M by the chemical structural formula of aluminate substrate fluorescent powder various raw materials synthesizing aluminate fluorescent material, regulate pH value to 2～5, stir, leave standstill and soak back centrifugal dewatering, wash again to supernatant liquor and be neutral;
(2) material by wet type mixing
Get NH
4F, HBO
3In at least a compound and BaF
2Mix to be dissolved in being washed till in the neutral phosphor raw material suspension with any weight ratio, stir, leave standstill the back oven dry as reaction promotor; The consumption of previous reaction promotor is 0.5～10% of a phosphor raw material weight;
(3) one times high temperature air is synthetic
The powder of oven dry is heated to 1300～1600 ℃ under air atmosphere, insulation 2～12h cools to room temperature with the furnace and comes out of the stove;
(4) crushing and classifications
With synthetic powder agglomates crushing and classification is the once-firing powder of≤3.5 μ m, D10 〉=1 μ m, D90≤7 μ m to medium particle diameter D50.
(5) secondary high temperature reduction
The synthetic powder that obtains of high temperature air is placed high temperature hydrogen furnace, be heated to 1200～1550 ℃, insulation 2～12h cools to room temperature with the furnace and comes out of the stove, and obtains fluorescent material;
(6) secondary classification
The fluorescent material that secondary reduction is obtained carries out classification once more, obtains the fluorescent material of medium particle diameter D50 for≤3.2 μ m, D10 〉=1 μ m, D90≤6 μ m;
(7) surface coats
With the fluorescent material after the secondary classification wash be neutrality to supernatant after, get 0.5～20% the MgCl that accounts for fluorescent material weight
2, be 0.2～10% phosphor suspension with the fluorescent material compound concentration, behind ultra-sonic dispersion, water bath heat preservation, stir into phosphor suspension; With volumetric molar concentration is the NH of 0.25～2M
3H
2O solution adds in the phosphor suspension in the dropping mode, the back finishes to drip in regulator solution pH value to 8～10 scopes, continue insulation and stir the back centrifugation, extremely neutral with washing, after dehydration, oven dry, in air, be heated to 200～400 ℃ again, insulation 30～120min, furnace cooling promptly obtains the aluminate fluorescent powder finished product that final surface is coated with the MgO film.
Acid solution is HNO described in the abovementioned steps (1)
3Or HCl solution, churning time is 30～240min, leaving standstill soak time is 6～48h, adopts distilled water or deionized water wash to supernatant liquor to be neutral.
After churning time in the abovementioned steps (2) was 30～300min, time of repose was 1～12h, and bake out temperature is 80～200 ℃.What the weight of reaction promotor accounted for the phosphor raw material gross weight in the step (2) preferably is 1～5%.
The described crushing and classification of abovementioned steps (4) is the synthetic powder at first to be added to adopt in the jaw crusher soon carry out a coarse crushing, again broken the pulverizing in the broken pulverizer of powder adding employing corundum roller that obtains of jaw further is crushed to pulverulence, at last the broken powder that obtains of roller added the jet mill grinding machine and carry out classification.Wherein jaw crusher preferably adopts the jaw crusher of corundum plate as liner.It is≤3.2 μ m that the medium particle diameter of the once-firing powder that crushing and classification obtains in the step (4) is preferably D50, D10 〉=1 μ m, D90≤6 μ m.
The described secondary classification of abovementioned steps (6) adopts air classifier to carry out.Obtaining medium particle diameter D50 is≤3.0 μ m, D10 〉=1 μ m, the fluorescent material of D90≤6 μ m.
Fluorescent material after adopting in the abovementioned steps (7) 40～100 ℃ deionized water or distilled water with classification washs to supernatant and is neutral; The time of ultra-sonic dispersion is 10～30min; The temperature of water bath heat preservation is 20～60 ℃, and the water-bath time is 30～120min; Adopt homogenizer to stir phosphor suspension with the rotating speed of 100～800rpm/min; NH
3H
2The drop rate of O solution is 2～50ml/min, and it is 0.5～6h that knot speed drips the follow-up continuation of insurance time warm and that stir; Extremely neutral after the centrifugation with deionized water wash, again with dehydrated alcohol dehydration, 80～150 ℃ of oven dry.
MgCl in the step (7)
2Account for fluorescent material weight and be preferably 2.5～7.5%.
Drip NH in the step (7)
3H
2O regulator solution pH value is preferably to 8～9.
The present invention has following advantage:
(1) adopts HNO
3Or the HCl aqueous solution anticipates under acidic conditions the raw material of synthetizing phosphor powder, can be to the used Al of synthetic aluminate fluorescent powder
2O
3, BaCO
3, MgO, Eu
2O
3And MnCO
3Surface functional group type and surfactivity thereof Deng raw material are regulated, and this will play very favorable effect for effectively reduce synthesis temperature in follow-up high temperature synthesis procedure.
(2) adopted NH especially
4F or H
3BO
3Deng compound that can be water-soluble as reaction promotor, NH
4F and H
3BO
3After the dissolving, the F that ionization produces
-Ion or BO
3 3-Ion can form even absorption at the powder surface of the pretreated fluorescent material synthesis material of peracidity, thus, can reduce the consumption of promotor significantly, avoids the synthetic powder that serious sintering or adhesion take place, and helps obtaining the tiny fluorescent material of particle diameter.
(3) adopt for twice air classifier to a synthetic powder of fluorescent material and the secondary reduction powder is pulverized, classification.On the one hand, because the principle of work of air-flowing type crushing and classification machine is the high velocity impact that relies between the powder, fragmentation reaches the purpose that reduces particle diameter, thereby just can effectively avoid or reduce surface crystallinity that ball mill the brought loss of tradition based on grinding.On the other hand, pass through air classification, also can be to meticulous in the powder or cross thick part powder and screen away, thus can effectively guarantee the distribution of fluorescent material medium particle diameter and particle diameter, this for the coating of satisfying the high definition plasma display and display requirement with highly beneficial.
(4) coat MgO by fluorescent material being carried out the surface, can effectively reduce the thermal degradation when that the coating operation of fluorescent material is brought.Reason is that the MgO film on fluorescent material top layer can effectively intercept the intrusion of extraneous oxygen [O] in the calcination process, thereby has avoided excitation center Mn in the fluorescent material
2+(or Eu
2+) be oxidized to Mn
3+(or Eu
3+); In the PDP working order, coating is also alleviated the work deterioration that irradiation brought of high-energy ion bombardment and vacuum ultraviolet ray (VUV), prolongs the working life of PDP.
(6),, can also play the effect that reduces the fluorescent material striking voltage, thereby cut down the consumption of energy therefore as coated fertilizer because MgO has higher secondary electron yield.
(7) advantage of the effective bonded high temperature solid-state method of present method, superfine powder pulverizing and technology such as classification technique and powder surface modification, technology is simple, is easy to control.With respect to wet methods such as co-precipitation, sol-gel, spray pyrolysis, manufacture method provided by the present invention is having more advantage aspect cost control and the production control, be easy to accomplish scale production.
Embodiment
Embodiment 1
1) raw materials pretreatment
According to Ba
0.85MgAl
10O
17: Eu
0.06Chemical structural formula, take by weighing BaCO respectively
313.98g, MgO 3.33g, Al
2O
341.67g, Eu
2O
30.88g.Placing volumetric molar concentration is the HNO of 0.2M
3In the aqueous solution, regulate pH value to 2, stir 30min after, leave standstill soak 6h after, centrifugal dewatering is used distilled water (or deionized water) to wash to supernatant liquor again and is neutrality.
2) material by wet type mixing
Take by weighing NH
4F (0.5～10%) 0.9g is dissolved in and is washed till in the neutral phosphor raw material suspension, behind the stirring 50min, leaves standstill 1h, 80 ℃ of oven dry.
3) high temperature air is synthetic
Place in the High Temperature Furnaces Heating Apparatus under air atmosphere, be heated to 1300 ℃, insulation 6h cools to room temperature with the furnace and comes out of the stove;
4) jet mill grinding
Adopt the corundum plate as carrying out a coarse crushing in the jaw crusher of liner the adding of the fast elder generation of the powder that burns till, more broken the pulverizing in the broken pulverizer of powder adding employing corundum roller that obtains of jaw further is crushed to pulverulence.At last the broken powder that obtains of roller is added the jet mill grinding machine, obtaining medium particle diameter (D50) is≤3.5 μ m, D10 〉=1 μ m, the once-firing powder of D90≤7 μ m.
5) secondary high temperature reduction
The synthetic powder that classification obtains is put into crucible, place high temperature hydrogen furnace, be heated to 1350 ℃, insulation 3h cools to room temperature with the furnace and comes out of the stove, and promptly obtains the fluorescent material that burns till.
(6) secondary classification
The fluorescent material that secondary reduction is obtained will adopt air classifier to carry out classification once more, and obtaining medium particle diameter (D50) is≤3.2 μ m, D10 〉=1 μ m, the fluorescent material of D90≤6 μ m.
(7) surface coats
After with deionized water (or distilled water) fluorescent material after the classification being neutrality with 60 ℃ deionized water wash to supernatant, take by weighing MgCl
2(0.29g 0.5～20%) is 0.5% phosphor suspension with the fluorescent material compound concentration, ultra-sonic dispersion 10min, and 50 ℃ of water bath heat preservations, with the rotating speed of 100rpm/min stir phosphor suspension on one side, will with volumetric molar concentration the NH of 0.25M on one side
3H
2O solution adds in the phosphor suspension with the speed of dripping of 3ml/min, regulator solution pH value to 8 stops ammonia soln and drips, and after continuing insulation and stirring 1h, centrifugation, to neutral, dewater 80 ℃ of oven dry with deionized water wash again with dehydrated alcohol, be heated to 200 ℃ in the air, insulation 30min, furnace cooling promptly obtains the aluminate blue fluorescent powder finished product that final surface is coated with the MgO film.
Embodiment 2
Handle raw material according to stoicheiometry identical and pretreatment technology, get NH with embodiment 1
4F0.15g and BaF
20.28g, in dispersion and the phosphor suspension, behind the stirring 30min, leave standstill 6h, 100 ℃ of oven dry are placed in the High Temperature Furnaces Heating Apparatus, and 1500 ℃ of insulation 4h cool to room temperature with the furnace and come out of the stove; Adopt the corundum plate as carrying out a coarse crushing in the jaw crusher of liner the adding of the fast elder generation of the powder that burns till, more broken the pulverizing in the broken pulverizer of powder adding employing corundum roller that obtains of jaw further is crushed to pulverulence.At last the broken powder that obtains of roller is added the jet mill grinding machine, obtaining medium particle diameter (D50) is≤3.5 μ m, D10 〉=1 μ m, the once-firing powder of D90≤7 μ m.The synthetic powder that classification obtains is put into crucible, place high temperature hydrogen furnace, 1450 ℃ of insulation 6h, cooling to room temperature with the furnace comes out of the stove, the fluorescent material that secondary reduction is obtained will adopt air classifier to carry out classification once more, obtaining medium particle diameter (D50) is≤3.2 μ m, D10 〉=1 μ m, the fluorescent material of D90≤6 μ m.
After with deionized water (or distilled water) fluorescent material after the classification being neutrality with 80 ℃ deionized water wash to supernatant, take by weighing MgCl
2(0.6g 0.5～20%) is 0.5% phosphor suspension with the fluorescent material compound concentration, ultra-sonic dispersion 10min, and 50 ℃ of water bath heat preservations, with the rotating speed of 400rpm/min stir phosphor suspension on one side, will with volumetric molar concentration the NH of 0.05M on one side
3H
2O solution adds in the phosphor suspension with the speed of dripping of 15ml/min, regulator solution pH value to 9 stops ammonia soln and drips, and after continuing insulation and stirring 1h, centrifugation, to neutral, dewater 120 ℃ of oven dry with deionized water wash again with dehydrated alcohol, be heated to 300 ℃ in the air, insulation 30min, furnace cooling promptly obtains the aluminate blue fluorescent powder finished product that final surface is coated with the MgO film.
Embodiment 3
Handle raw material according to stoicheiometry identical and pretreatment technology, get NH with embodiment 1
4F1.2g and H
3BO
32.5g, in dispersion and the phosphor suspension, behind the stirring 30min, leave standstill 12h, 100 ℃ of oven dry are placed in the High Temperature Furnaces Heating Apparatus, and 1550 ℃ of insulation 3h cool to room temperature with the furnace and come out of the stove; Adopt the corundum plate as carrying out a coarse crushing in the jaw crusher of liner the adding of the fast elder generation of the powder that burns till, more broken the pulverizing in the broken pulverizer of powder adding employing corundum roller that obtains of jaw further is crushed to pulverulence.At last the broken powder that obtains of roller is added the jet mill grinding machine, obtaining medium particle diameter (D50) is≤3.5 μ m, D10 〉=1 μ m, the once-firing powder of D90≤7 μ m.The synthetic powder that classification obtains is put into crucible, place high temperature hydrogen furnace, 1400 ℃ of insulation 3h, cooling to room temperature with the furnace comes out of the stove, the fluorescent material that secondary reduction is obtained will adopt air classifier to carry out classification once more, obtaining medium particle diameter (D50) is≤3.2 μ m, D10 〉=1 μ m, the fluorescent material of D90≤6 μ m.
After with deionized water (or distilled water) fluorescent material after the classification being neutrality with 100 ℃ deionized water wash to supernatant, take by weighing MgCl
2(2.85g 0.5～20%) is 2.5% phosphor suspension with the fluorescent material compound concentration, ultra-sonic dispersion, and 80 ℃ of water bath heat preservations, with the rotating speed of 400rpm/min stir phosphor suspension on one side, will with volumetric molar concentration the NH of 0.05M on one side
3H
2O solution adds in the phosphor suspension with the speed of dripping of 6ml/min, regulator solution pH value to 10 stops ammonia soln and drips, and after continuing insulation and stirring 6h, centrifugation, to neutral, dewater 120 ℃ of oven dry with deionized water wash again with dehydrated alcohol, be heated to 300 ℃ in the air, insulation 60min, furnace cooling promptly obtains the aluminate blue fluorescent powder finished product that final surface is coated with the MgO film.
Embodiment 4
1) raw materials pretreatment
According to Ba
0.95Mg
0.82Al
12O
19: Mn
0.15Chemical structural formula, take by weighing BaCO respectively
315.62g, MgO 2.73g, Al
2O
350.5g, MnCO
31.44g.Placing volumetric molar concentration is the HNO of 0.1M
3In the aqueous solution, regulate pH value to 3, stir 60min after, leave standstill soak 6h after, centrifugal dewatering is used distilled water (or deionized water) to wash to supernatant liquor again and is neutrality.
2) material by wet type mixing
Take by weighing NH
4F (0.5～10%) 1.41g is washed till in the neutral phosphor raw material suspension with being dissolved in, and behind the stirring 50min, leaves standstill 3h, 80 ℃ of oven dry.
3) high temperature air is synthetic
Place in the High Temperature Furnaces Heating Apparatus under air atmosphere, be heated to 1550 ℃, insulation 8h cools to room temperature with the furnace and comes out of the stove;
4) jet mill grinding
Adopt the corundum plate as carrying out a coarse crushing in the jaw crusher of liner the adding of the fast elder generation of the powder that burns till, more broken the pulverizing in the broken pulverizer of powder adding employing corundum roller that obtains of jaw further is crushed to pulverulence.At last the broken powder that obtains of roller is added the jet mill grinding machine, obtaining medium particle diameter (D50) is≤3.5 μ m, D10 〉=1 μ m, the once-firing powder of D90≤7 μ m.
5) secondary high temperature reduction
The synthetic powder that classification obtains is put into crucible, place high temperature hydrogen furnace, be heated to 1450 ℃, insulation 6h cools to room temperature with the furnace and comes out of the stove, and promptly obtains the fluorescent material that burns till.
(6) secondary classification
The fluorescent material that secondary reduction is obtained will adopt air classifier to carry out classification once more, and obtaining medium particle diameter (D50) is≤3.2 μ m, D10 〉=1 μ m, the fluorescent material of D90≤6 μ m.
(7) surface coats
After with deionized water (or distilled water) fluorescent material after the classification being neutrality with 80 ℃ deionized water wash to supernatant, take by weighing MgCl
2(3.33g 0.5～20%) is 1.5% phosphor suspension with the fluorescent material compound concentration, ultra-sonic dispersion 10min, and 50 ℃ of water bath heat preservations, with the rotating speed of 100rpm/min stir phosphor suspension on one side, will with volumetric molar concentration the NH of 0.25M on one side
3H
2O solution adds in the phosphor suspension with the speed of dripping of 3ml/min, regulator solution pH value to 8 stops ammonia soln and drips, and after continuing insulation and stirring 3h, centrifugation, to neutral, dewater 80 ℃ of oven dry with deionized water wash again with dehydrated alcohol, be heated to 200 ℃ in the air, insulation 30min, furnace cooling promptly obtains the aluminate green fluorescent powder finished product that final surface is coated with the MgO film.
Embodiment 5
Obtaining medium particle diameter (D50) according to the composition identical with embodiment 4 and the synthesis technique production in (1)～(6) step is≤3.2 μ m, D10 〉=1 μ m, the fluorescent material of D90≤6 μ m.After with deionized water (or distilled water) fluorescent material after the classification being neutrality with 60 ℃ deionized water wash to supernatant, take by weighing MgCl
2(4.56g 0.5～20%) is 1.0% phosphor suspension with the fluorescent material compound concentration, ultra-sonic dispersion 15min, and 60 ℃ of water bath heat preservations, with the rotating speed of 100rpm/min stir phosphor suspension on one side, will with volumetric molar concentration the NH of 0.2M on one side
3H
2O solution adds in the phosphor suspension with the speed of dripping of 5ml/min, regulator solution pH value to 9 stops ammonia soln and drips, and after continuing insulation and stirring 6h, centrifugation, to neutral, dewater 80 ℃ of oven dry with deionized water wash again with dehydrated alcohol, be heated to 350 ℃ in the air, insulation 30min, furnace cooling promptly obtains the aluminate green fluorescent powder finished product that final surface is coated with the MgO film.
Claims (10)
1. the manufacture method of an aluminate substrate fluorescent powder is characterized in that the manufacturing of fluorescent material may further comprise the steps:
(1) raw materials pretreatment
Be distributed in the acid solution that volumetric molar concentration is 0.1M～2.0M by the chemical structural formula of aluminate substrate fluorescent powder various raw materials synthesizing aluminate fluorescent material, regulate pH value to 2～5, stir, leave standstill and soak back centrifugal dewatering, wash again to supernatant liquor and be neutral;
(2) material by wet type mixing
Get NH
4F, HBO
3In at least a compound and BaF
2Mix to be dissolved in being washed till in the neutral phosphor raw material suspension with any weight ratio, stir, leave standstill the back oven dry as reaction promotor; The consumption of previous reaction promotor is 0.5～10% of a phosphor raw material weight;
(3) one times high temperature air is synthetic
The powder of oven dry is heated to 1300～1600 ℃ under air atmosphere, insulation 2～12h cools to room temperature with the furnace and comes out of the stove;
(4) crushing and classifications
With synthetic powder agglomates crushing and classification is the once-firing powder of≤3.5 μ m, D10 〉=1 μ m, D90≤7 μ m to medium particle diameter D50.
(5) secondary high temperature reduction
The synthetic powder that obtains of high temperature air is placed high temperature hydrogen furnace, be heated to 1200～1550 ℃, insulation 2～12h cools to room temperature with the furnace and comes out of the stove, and obtains fluorescent material;
(6) secondary classification
The fluorescent material that secondary reduction is obtained carries out classification once more, obtains the fluorescent material of medium particle diameter D50 for≤3.2 μ m, D10 〉=1 μ m, D90≤6 μ m;
(7) surface coats
With the fluorescent material after the secondary classification wash be neutrality to supernatant after, get 0.5～20% the MgCl that accounts for fluorescent material weight
2, be 0.2～10% phosphor suspension with the fluorescent material compound concentration, behind ultra-sonic dispersion, water bath heat preservation, stir into phosphor suspension; With volumetric molar concentration is the NH of 0.25～2M
3H
2O solution adds in the phosphor suspension in the dropping mode, the back finishes to drip in regulator solution pH value to 8～10 scopes, continue insulation and stir the back centrifugation, extremely neutral with washing, after dehydration, oven dry, in air, be heated to 200～400 ℃ again, insulation 30～120min, furnace cooling promptly obtains the aluminate fluorescent powder finished product that final surface is coated with the MgO film.
2. according to the manufacture method of the described aluminate substrate fluorescent powder of claim 1, it is characterized in that acid solution is HNO described in the step (1)
3Or HCl solution, churning time is 30～240min, leaving standstill soak time is 6～48h, adopts distilled water or deionized water wash to supernatant liquor to be neutral.
3. according to the manufacture method of the described aluminate substrate fluorescent powder of claim 1, it is characterized in that churning time in the step (2) is 30～300min after, time of repose is 1～12h, bake out temperature is 80～200 ℃.
4. according to the manufacture method of claim 1 or 3 described aluminate substrate fluorescent powders, the weight of its feature reaction promotor in step (2) accounts for 1～5% of phosphor raw material gross weight.
5. according to the manufacture method of the described aluminate substrate fluorescent powder of claim 1, it is characterized in that the described crushing and classification of step (4) is the synthetic powder at first to be added to adopt in the jaw crusher soon carry out a coarse crushing, again broken the pulverizing in the broken pulverizer of powder adding employing corundum roller that obtains of jaw further is crushed to pulverulence, at last the broken powder that obtains of roller added the jet mill grinding machine and carry out classification.
6. according to the manufacture method of claim 1 or 5 described aluminate substrate fluorescent powders, it is characterized in that the medium particle diameter D50 of the once-firing powder that crushing and classification obtains in the step (4) is≤3.2 μ m, D10 〉=1 μ m, D90≤6 μ m.
7. according to the manufacture method of the described aluminate substrate fluorescent powder of claim 1, it is characterized in that the described secondary classification employing of step (6) air classifier carries out.Obtaining medium particle diameter D50 is≤3.0 μ m, D10 〉=1 μ m, the fluorescent material of D90≤6 μ m.
8. according to the manufacture method of the described aluminate substrate fluorescent powder of claim 1, the fluorescent material after it is characterized in that adopting in the step (7) 40～100 ℃ deionized water or distilled water with classification washs to supernatant and is neutral; The time of ultra-sonic dispersion is 10～30min; The temperature of water bath heat preservation is 20～60 ℃, and the time is 30～120min; Adopt homogenizer to stir phosphor suspension with the rotating speed of 100～800rpm/min; NH
3H
2The drop rate of O solution is 2～50ml/min, and it is 0.5～6h that knot speed drips the follow-up continuation of insurance time warm and that stir; Extremely neutral after the centrifugation with deionized water wash, again with dehydrated alcohol dehydration, 80～150 ℃ of oven dry.
9. according to the manufacture method of claim 1 or 8 described aluminate substrate fluorescent powders, it is characterized in that MgCl in step (7)
2Account for 2.5～7.5% of fluorescent material weight.
10. according to the manufacture method of claim 1 or 8 described aluminate substrate fluorescent powders, it is characterized in that dripping in the step (7) NH
3H
2O regulator solution pH value to 8～9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101911223A CN101182413B (en) | 2007-12-07 | 2007-12-07 | Method for preparing rare earth aluminate matrix fluorescent powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101911223A CN101182413B (en) | 2007-12-07 | 2007-12-07 | Method for preparing rare earth aluminate matrix fluorescent powder |
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| CN111234820B (en) * | 2020-03-06 | 2022-11-11 | 英特美光电（苏州）有限公司 | Preparation method of silicate fluorescent powder |
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