CN100441658C - Method of preparing yttrium aluminium garnet fluorescent powder - Google Patents
Method of preparing yttrium aluminium garnet fluorescent powder Download PDFInfo
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- CN100441658C CN100441658C CNB2007100197077A CN200710019707A CN100441658C CN 100441658 C CN100441658 C CN 100441658C CN B2007100197077 A CNB2007100197077 A CN B2007100197077A CN 200710019707 A CN200710019707 A CN 200710019707A CN 100441658 C CN100441658 C CN 100441658C
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- fluorescent powder
- aluminium garnet
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Abstract
The invention discloses a making method of fluorescent powder of yttrium aluminium garnet, which comprises the following steps: allocating certain quantity of alumina powder, yttrium nitrate, cerous nitrate and gadolinium nitrate into sediment mother liquid; allocating sediment agent solution through at least one of NaOH, NH3.H2O or NH3HCO3; maintaining sediment mother liquid temperature between 10 and 70 deg.c; stirring evenly; adding sediment agent solution into sediment mother liquid; stopping adding sediment agent when pH value is 6.8-11; insulating and stirring; separating solid from liquid of sediment mother liquid; washing solid through clean water; drying; adding fluoride in the powder as reacting adjuvant; placing blended powder into high-temperature stove; heating protected by gas; cooling; obtaining sintered fluorescent powder bulk; grinding; sieving; obtaining the product.
Description
One, technical field
The invention belongs to the manufacture method of fluorescent material, particularly a kind of manufacture method of yttrium aluminium garnet fluorescent powder.
Two, background technology
Prior art: yttrium aluminum garnet Y
3Al
5O
12Be a kind of important luminescent material matrix, advantages such as chemical stability is good, radiation hardness that it has.Cerium activated yttrium aluminium garnet YAG: Ce wherein
3+(YAG), excitation wavelength can effectively absorb the blue light that GaN photodiode (LED) sends near 460nm, and its emission wavelength can obtain high-brightness white-light with the blue light of LED is compound about 540nm.In order further to improve the various aspects of performance of fluorescent material, also need to wherein mixing other rare earth ion.This also is present unique fluorescent material that can enter the practical stage.
At present, this class fluorescent material all adopts high-temperature solid phase reaction method and coprecipitation method basically.The structural formula of mentioning as patent US6614179B1 is (Re
1-rSm
r)
3(Al
1-sGa
s)
5O
12: Ce, (0≤r≤1 wherein; 0≤s≤1, Re is Y or Gd) yttrium aluminum garnet system fluorescent material, promptly adopt high temperature solid-state method and coprecipitation method to carry out the preparation of YAG fluorescent material.For high temperature solid-state method, because the general Al that adopts more
2O
3, Y
2O
3, CeO
2, Ga
2O
3As initial feed,, finally must can obtain final product Deng the oxide compound that constitutes element through high-intensity mechanical disintegration and sub-sieve after that batch mixing and high temperature sintering obtain agglomerated powder is fast.And based on the relation between light-emitting phosphor performance and its surface crystallinity as can be known, the degree of perfection of the degree of crystallinity on fluorescent powder grain surface has conclusive effect to its luminescent properties.And for YAG fluorescent material, even under the prerequisite of adding solubility promoter, generally also need to be heated to about 1500 ℃, just can finish the doping of the synthetic and trace element of matrix.Thereby cause the fluorescent material sintering serious, follow-up mechanical disintegration operation then can cause the surface crystallinity havoc of fluorescent material, finally causes the obvious decline of light-emitting phosphor performance.
And coprecipitation method although can obtain more significantly to improve, had both comprised elements such as rare earth element y, La, Ce, Gd owing to constitute the element of YAG fluorescent material on morphology microstructure, also comprised elements such as Ga, In simultaneously.Want to realize the coprecipitation of all elements, on technology controlling and process, exist sizable difficulty, be difficult to ensure the stability and the consistence of the finished product performance.
In addition, also have, but aspect technology controlling and process and microscopic appearance, still exist obviously not enough such as wet chemical preparation methods such as Sol-Gel method and spray pyrolysis.
This shows that development of new YAG:Ce fluorescent material and preparation method thereof further improves the luminescent properties of fluorescent material, remains the important topic of demanding urgently studying.
Three, summary of the invention
The present invention is directed to above-mentioned technical problem, provide that a kind of synthesis temperature is low, the powder surface degree of injury is little, purity is high and can effectively control the manufacture method of the yttrium aluminium garnet fluorescent powder of powder appearance.
In order to achieve the above object, technical scheme provided by the invention is: alumina powder, Yttrium trinitrate, cerous nitrate and Gadolinium trinitrate that the fluorescent material stoichiometric ratio that (1) is mentioned according to referenced patents in the background technology takes by weighing corresponding weight are made into the suspension that total concn is 0.2～5M, as mother liquor of precipitation of ammonium, wherein alumina powder powder medium particle diameter is 200nm～5 μ m; (2) select NaOH, NH for use
3H
2O or NH
4HCO
3In at least aly be mixed with the precipitant solution that total concn is 0.01～2M; (3) the mother liquor of precipitation of ammonium temperature maintenance that step (1) is made is at 10～70 ℃, stir mother liquor of precipitation of ammonium with 50～500rpm speed, the precipitant solution that step (2) is made joins in the mother liquor of precipitation of ammonium by the flow velocity of 5～500mL/min, the pH value for the treatment of mother liquor reaches at 6.8～11 o'clock, stop to add precipitant solution, and continue insulation and stir 30～240min; (4) will precipitate the mother liquor that finishes through step (3) and pass through solid-liquid separation, water cleaning gained solid 2～4 times, dehydration again, dry under 60～120 ℃ then, the water ratio that makes powder is less than 0.25% of powder gross weight; (5) add fluorochemical in the powder after oven dry as reaction promoter, the consumption of auxiliary agent is 0.02～10% of an xeraphium body weight, stirs; (6) mixed powder is placed in the high-temperature atmosphere furnace, adopt CO or N
2-H
2Mixed gas is as protective atmosphere, be heated to 1000～1600 ℃ after, continue insulation 2～24h, come out of the stove after the cooling, the sintering fluorescent powder.(7) refrigerative sintering powder is pulverized by traditional technology, sub-sieve finally obtains fluorescent material.
Compared with prior art, the present invention has following advantage:
(1) compares with high temperature solid-state method, because other water insoluble nonionic salt sedimentations that adopt other formation fluorescent material that liquid-phase precipitation method will be except that Al are to Al
2O
3Particle surface, thereby can guarantee blended homogeneity between each component, obviously be better than the batch mixing homogeneity of the solid phase powder of solid phase method, make the synthetic temperature be able to obvious reduction thus, reduce to 1300 ℃ by the synthesis temperature of about 1550 ℃ of solid phase methods.
(2) because the reduction of synthesis temperature, thereby the sintering degree of powder obviously reduces, and the powder after burning till is loose soon, and sintering hardness obviously descends.Only need more weak mechanical disintegration can reach the requirement of use.Thereby the degree of injury of powder surface to be obviously descending thereupon, thereby guaranteed higher luminescent properties.
(3) coprecipitation method, Sol-Gel or spray pyrolysis etc. are finished each component blended synthesis technique under liquid-phase condition, owing to generally all need to select for use aluminum nitrate as synthesis material, and highly purified aluminum nitrate is difficult to obtain, general aluminum nitrate purity only can reach 98.0%, thereby cause Fe, Co, Ni etc. that the impurity that fluorescent material can produce quenching effect is brought into wherein, have a strong impact on the luminescent properties of final fluorescent material.Even and from can purchasing high-purity aluminum nitrate abroad, but too expensive and productive rate is crossed and lowly can't be satisfied actual production because of price.And preparation method provided by the invention, owing to directly adopt high purity (purity reaches 99.99%), thereby effectively avoided pollution problem.
When (4) adopting method such as coprecipitation method and Sol-Gel, Al
3+Ion generally all is to avale with the form of aluminium colloidal sol, although the Al (OH) that avales and in precipitation process
3The primary particles granularity can reach nano level, but in solid phase calcination process subsequently, owing to contain a large amount of crystal water, serious reunion and sintering very easily takes place, thereby can't control effectively to morphology microstructure.And preparation method of the present invention can select the good ultra-fine Al of sphericity for use
2O
3, avoided sintering, obtained good microscopic appearance simultaneously again.(see figure 1)
Four, description of drawings
Fig. 1 is Y
2.87Al
5O
12: Ce
0.13The microscopic appearance photo.As can be seen from this figure, the MODEL OF THE PHOSPHOR PARTICLE SIZE that adopts the present invention to make is tiny evenly to need not mechanical disintegration, can satisfy actual service requirements.
Five, embodiment
Embodiment 1
(1) ultra-fine alumina powder, Yttrium trinitrate, cerous nitrate and the Gadolinium trinitrate that takes by weighing corresponding weight according to the fluorescent material stoichiometric ratio is made into total concn and can be 0.25,0.73,0.12,0.28,0.37 or the Al of 4.5M
2O
3Suspension.
(2) select NaOH, NH for use
3H
2O and NH
4HCO
3In at least a total concn that is made into be 0.03,0.05,0.08,1.25,1.59 or the solution of 1.9M, as precipitation agent.
(3) will prepare the mother liquor of precipitation of ammonium temperature is controlled in 15,25,30,42,55 or 65 ℃ of scopes, with 50,90,150,260,330 or 460rpm speed stirred suspension, simultaneously with precipitant solution by 34,80,240,365,470 or the flow velocity of 500mL/min join Al
2O
3In the suspension, treat that mother liquor pH value reaches at 6.8～11 o'clock, stop reinforced process, and continue insulation and stir 30,60,120,180 or 240min.
(4) will precipitate the mother liquor centrifugation that finishes, again with deionized water washing 2～4 times, dehydration, then 60～120 ℃ of oven dry down, and the water ratio that makes powder is less than 0.25%.
5) add 0.1,0.5,1.5,3.8,5.5,6.9,8.2% NH in the powder after oven dry with respect to oven dry powder total amount
4F, AlF
3, BaF
2Or NH
4HF
2As reaction promoter, mix;
6) mixed powder is placed in the high-temperature atmosphere furnace, with N
2-H
2Mixed gas is heated to 1200,1350,1400,1450 or 1600 ℃ as protective atmosphere, continues insulation 2,4,6,10,15,20 or 24h, comes out of the stove after the cooling.
7) refrigerative sintering powder is pulverized, sub-sieve finally obtains fluorescent material.
Embodiment 2
(1) takes by weighing Al
2O
325.5g, Ce (NO
3)
26H
2O 5.65g, Y
2O
332.40g, with Y
2O
3Be dissolved in the concentrated nitric acid that 50ml concentration is 5M, 90 ℃ of heating concentrate and obtain white transparent Y (NO
3)
36H
2The O xln, with deionized water with Al
2O
3, Ce (NO
3)
26H
2O and Y (NO
3)
36H
2O is made into the suspension of 0.6M, and is heated to 25 ℃.Take by weighing NH again
4HCO
3It is 25% aqueous solution that 120g is made into concentration.Rotating speed with 120rpm stirs Al on one side
2O
3Suspension, Yi Bian with NH
4HCO
3Solution adds Al with the flow velocity of 25mL/min
2O
3In the suspension, treat that the pH value of suspension reaches at 8.2 o'clock, stop to feed in raw material, continue to stir insulation 120min, centrifugation, deionization washing, dehydrated alcohol dehydration, 90 ℃ of oven dry.Place high temperature reduction atmosphere furnace internal heating to 1350 ℃ again, insulation 10h will cool off back powder pulverizing, sub-sieve, and obtaining molecular structural formula is Y
2.87Al
5O
12: Ce
0.13, its microscopic appearance is seen Fig. 1.
Embodiment 3
(1) takes by weighing Al
2O
325.5g, Ce (NO
3)
26H
2O 4.78g, Y
2O
333.08g, with Y
2O
3Be dissolved in the concentrated nitric acid that 50ml concentration is 5M, 90 ℃ of heating concentrate and obtain white transparent Y (NO
3)
36H
2The O xln, with deionized water with Al
2O
3, Ce (NO
3)
26H
2O and Y (NO
3)
36H
2O is made into the suspension of 0.6M, and is heated to 25 ℃.Taking by weighing NaOH 20g again, to be made into concentration be 10% aqueous solution.Rotating speed with 120rpm stirs Al on one side
2O
3Suspension, Yi Bian with NH
4HCO
3Solution adds Al with the flow velocity of 16mL/min
2O
3In the suspension, treat that the pH value of suspension reaches at 8.5 o'clock, stop to feed in raw material, continue to stir insulation 120min, centrifugation, deionization washing, dehydrated alcohol dehydration, 90 ℃ of oven dry.Place high temperature reduction atmosphere furnace internal heating to 1400 ℃ again, insulation 6h will cool off back powder pulverizing, and sub-sieve obtains Y
2.89Al
5O
12: Ce
0.11
Claims (8)
1. the manufacture method of a yttrium aluminium garnet fluorescent powder is characterized in that preparation process is:
A. be made into the suspension that total concn is 0.2～5M according to conventional fluorescent material stoichiometric ratio preparation Yttrium trinitrate, alumina powder, cerous nitrate, as mother liquor of precipitation of ammonium, wherein alumina powder powder medium particle diameter is 200nm～5 μ m;
B. select NaOH, NH for use
3H
2O or NH
4HCO
3In at least aly be mixed with the precipitant solution that total concn is 0.01～2M;
C. the mother liquor of precipitation of ammonium temperature maintenance that step a is made is at 10～70 ℃, stir mother liquor of precipitation of ammonium with 50～500rpm speed, the precipitant solution that step b is made joins in the mother liquor of precipitation of ammonium by the flow velocity of 5～500mL/min, the pH value for the treatment of mother liquor reaches at 6.8～11 o'clock, stop to add precipitant solution, and continue insulation and stir 30～240min;
D. will be through the mother liquor solid-liquid separation of step c precipitation end, water cleaning gained solid 2～4 times, dehydration again, dry under 60～120 ℃ then, the water ratio that makes powder is less than 0.25% of powder gross weight;
E. add fluorochemical as reaction promoter in dried powder, the consumption of auxiliary agent is 0.02～10% of an xeraphium body weight, stirs;
F. mixed powder is placed in the high-temperature atmosphere furnace, adopt CO or N
2-H
2Mixed gas is as protective atmosphere, be heated to 1000～1600 ℃ after, continue insulation 2～24h, come out of the stove after the cooling, the sintering fluorescent powder;
G. refrigerative sintering powder is pulverized by traditional technology, sub-sieve finally obtains fluorescent material.
2. the manufacture method of yttrium aluminium garnet fluorescent powder according to claim 1 is characterized in that the suspension concentration that ultra-fine alumina, Yttrium trinitrate, cerous nitrate and Gadolinium trinitrate are made into is 0.5～2.5M.
3. the manufacture method of yttrium aluminium garnet fluorescent powder according to claim 1, the pH titration that it is characterized in that mother liquor is 7.5～8.5.
4. the manufacture method of yttrium aluminium garnet fluorescent powder according to claim 1, it is characterized in that reinforced the end after, continue insulation and time of stirring is 60～120min.
5. the manufacture method of yttrium aluminium garnet fluorescent powder according to claim 1 is characterized in that reaction promoter is Neutral ammonium fluoride, barium fluoride or aluminum fluoride.
6. the manufacture method of yttrium aluminium garnet fluorescent powder according to claim 1, the consumption that it is characterized in that reaction promoter is that the ratio of raw material gross weight is 0.5～2.5%.
7. the manufacture method of yttrium aluminium garnet fluorescent powder according to claim 1 is characterized in that Heating temperature is 1200～1400 ℃.
8. the manufacture method of yttrium aluminium garnet fluorescent powder according to claim 1 is characterized in that calcination time is 3～5h.
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| CN100441658C true CN100441658C (en) | 2008-12-10 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101182413B (en) * | 2007-12-07 | 2010-12-01 | 江苏苏博特新材料股份有限公司 | Method for preparing rare earth aluminate matrix fluorescent powder |
| CN101973569B (en) * | 2010-10-15 | 2012-09-26 | 河南理工大学 | Method for synthesizing fluorescent powder of yttrium aluminum garnet |
| CN107686350B (en) * | 2016-08-03 | 2021-04-30 | 深圳光峰科技股份有限公司 | Preparation method of Ce-doped YAG luminescent ceramic |
| CN111574215B (en) * | 2020-05-26 | 2022-02-08 | 莆田学院 | Method for preparing yttrium aluminum garnet powder |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5464568A (en) * | 1993-11-24 | 1995-11-07 | Eastman Kodak Company | Alkaline earth metal fluorobromoiodide storage phosphor, and radiation image storage panel, and method |
| CN1792805A (en) * | 2005-11-25 | 2006-06-28 | 中国科学院上海光学精密机械研究所 | Process for preparing yttrium aluminium garnet nano powder |
| CN1844305A (en) * | 2006-04-14 | 2006-10-11 | 厦门大学 | Process for preparing yttrium aluminum garnet |
-
2007
- 2007-02-06 CN CNB2007100197077A patent/CN100441658C/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5464568A (en) * | 1993-11-24 | 1995-11-07 | Eastman Kodak Company | Alkaline earth metal fluorobromoiodide storage phosphor, and radiation image storage panel, and method |
| CN1792805A (en) * | 2005-11-25 | 2006-06-28 | 中国科学院上海光学精密机械研究所 | Process for preparing yttrium aluminium garnet nano powder |
| CN1844305A (en) * | 2006-04-14 | 2006-10-11 | 厦门大学 | Process for preparing yttrium aluminum garnet |
Non-Patent Citations (2)
| Title |
|---|
| 共沉淀法制备YAG超细粉及透明陶瓷. 闻雷等.功能材料，第35卷第1期. 2004 |
| 共沉淀法制备YAG超细粉及透明陶瓷. 闻雷等.功能材料，第35卷第1期. 2004 * |
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