CN1189535C - Method for preparing blue luminescent powder of aluminate activated by vacuum ultraviolet radiation - Google Patents
Method for preparing blue luminescent powder of aluminate activated by vacuum ultraviolet radiation Download PDFInfo
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- CN1189535C CN1189535C CNB021553211A CN02155321A CN1189535C CN 1189535 C CN1189535 C CN 1189535C CN B021553211 A CNB021553211 A CN B021553211A CN 02155321 A CN02155321 A CN 02155321A CN 1189535 C CN1189535 C CN 1189535C
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- calcination
- ultraviolet rays
- barium
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Abstract
The present invention relates to a preparation method for blue aluminate fluorescent powder activated by vacuum ultraviolet rays. The blue fluorescent body activated by vacuum ultraviolet rays is aluminate activated by Eu<2+> and has the empirical formula of Ba1-xEuxMgAl10O17, wherein x is less than or equal to 0.2 and more than or equal to 0.02. The preparation method comprises the steps of the selection of raw materials and fluxing agents, the generation of a reducing atmosphere and the control of the reaction temperature and the reaction time. The green high-efficiency fluorescent body emits blue light under the excitation of vacuum ultraviolet rays and can be used for displays and lumination devices such as plasma panel displays, rare gas lamps, etc.
Description
Technical field
The present invention relates to the preparation method of the aluminate blue fluorescent body that a kind of vacuum ultraviolet rays excites.
Background technology
In recent years, vacuum ultraviolet rays excites down luminescent device to obtain development widely, and its mechanism is by rare gas Xe, Ne-Xe, the vacuum ultraviolet rays excited fluophor visible emitting that produces thereby Ar etc. discharge.Vacuum ultraviolet rays excites down luminescent device Chromatic color large-screen high-resolution degree plasma panel display (PDP), non-mercury florescent lamp etc., PDP utilizes vacuum ultraviolet rays to excite different fluor generations red, green, thereby the light color image display of blue three kinds of different colours, it is little that PDP has a volume, thin thickness and image fidelity, and the advantage of easily making flat pannel display such as big area, and PDP makes the digitizing that shows image by the regulation and control of 8 byte digital gray scales, representing the developing direction of following information and demonstration, will be at digitized high definition television (HDTV), all many-sides such as graphoscope are widely used.And non-mercury florescent lamp utilizes the vacuum ultraviolet rays excited fluophor luminous, because its discharge gas is rare gas, mostly excites with the mercury ionizing ray with at present used luminescent lamp and to compare, and can not cause environmental pollution in the process of producing and using.Therefore, it is with possible green illumination light source as future.For this reason, people are developing and are utilizing Xe, Ne-Xe, the non-mercury florescent lamp that the vacuum ultraviolet rays that noble gas discharges such as Ar produce excites.
Since the seventies, people have been developed some high-efficiency vacuum ultraviolet rays excited fluorescent bodies.As be used for the three-color phosphor of PDP: red-emitting phosphors (Y, Gd) BO
3: Eu, green-emitting phosphor Zn
2SiO
4: Mn and BaAl
12O
19: Mn, blue emitting phophor BaMgAl
10O
17: Eu and BaMgAl
14O
23: Eu etc.These vacuum ultraviolet luminescent materials the preparation method be the important directions that people study always.
Divalent europium activates barium magnesium aluminate, its structure is the beta-alumina structure, divalent europium replaces barium ion in aluminate, under the vacuum-ultraviolet light irradiation, the matrix absorption vacuum ultraviolet rays is also given divalent europium transmission ofenergy, the electronics of europium ion is on the higher excited level, and electronics relaxes towards on the minimum excited level by radiationless then, and last electronics transits to ground state from minimum excited level and launches blue light.Need reducing atmosphere owing to obtain divalent europium, the formation of barium magnesium aluminate needs reaction at high temperature, and therefore, its preparation will be carried out in high temperature reduction atmosphere.The reducing atmosphere that generally adopts is the mixed gas of nitrogen and hydrogen at present.High efficient luminous material Ba is disclosed as U.S. Pat 6096243
1-xEu
xMgAl
10O
17Preparation method, the atmosphere that it adopts are the mixed gass of nitrogen and hydrogen.Adopt the mixed gas calcination conditional request strictness of nitrogen and hydrogen, calcination time is long, and whole preparation cycle is long, and preparation cost is higher, and in preparation process owing to the existence of hydrogen, set off an explosion easily.Middle Chinese patent CN1190115A discloses BaMgAl
14O
23: the preparation method of Eu, this patent directly cover carbon dust on the starting material, and this preparation method's causes the Prevent Carbon Contamination of the part of fluorescent material, thereby cause the waste of starting material in preparation process because carbon dust is directly to contact with starting material.Therefore, this preparation method can not satisfy demand of practical production well.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of vacuum ultraviolet rays activated blue aluminate fluorescent powder.Adopt two crucible graphite or carbon reduction method preparation, wanting the reductive sample to be placed in the interior crucible, and put non-tight lid at interior crucible, graphite or carbon are put between outer crucible and the crucible, outer crucible covers sealing cover, puts into High Temperature Furnaces Heating Apparatus then, and calcination at high temperature produces reducing atmosphere, with the sample reduction, thereby make needed high efficient luminous material.
The chemical formula that the present invention relates to the barium magnesium aluminate blue emitting phophor is:
Ba
1-xEu
xMgAl
10O
17，
0.04≤x≤0.2 wherein
The starting material that adopted are: europium sesquioxide; Barium oxide maybe can transform one or both compounds in the barium carbonate of corresponding oxide or the barium oxalate; Magnesium oxide maybe can transform in magnesium hydroxide, magnesiumcarbonate or the magnesium oxalate of corresponding oxide one or more; Aluminum oxide maybe can transform in the aluminium hydroxide of corresponding oxide one or both;
Fusing assistant is 0～6% mole of boric acid, Neutral ammonium fluoride, aluminum fluoride, magnesium fluoride or barium fluoride, and wherein one or more or do not add fusing assistant;
To put into graphite or carbon calcination between outer crucible and the interior crucible, calcination temperature is 1400～1700 ℃; Calcination time is 1～8 hour; The calcination number of times is for once or secondary; Cooling is taken out, and gets powdery phosphor through crushing screening, and 147nm excites down, and luminosity is greater than 100.
Adopt the present invention to prepare high-efficiency vacuum ultraviolet rays activated barium magnesium aluminate blue emitting phophor following characteristics arranged:
1, when the above-mentioned luminescent material of preparation, crucible is a high temperature sintering in air, and preparation technology is simple, and is safe and reliable, and working condition is controlled easily, and is with short production cycle, and cost is low.
2, owing to adopt two crucible reduction, sample and graphite or carbon are separated, can either prevent the pollution of graphite or carbon effectively, can effectively go back raw sample again simultaneously, therefore can obtain high efficient luminous material.
3, can heat continuously, a large amount of save energy reduce production costs.
Embodiment
Embodiment 1
Take by weighing BaCO
30.09 mole, Al
2O
30.5 mole, 0.1 mole of MgO, Eu
2O
30.005 mole, H
3BO
30.005 mole utilizes ball mill to carry out abundant ground and mixed, puts into a less alumina crucible, cover the non-tight lid, then it is put into a bigger alumina crucible, graphite or carbon are put between outer crucible and the crucible, outer crucible covers sealing cover, puts into High Temperature Furnaces Heating Apparatus, 1450 ℃, calcination 5 hours, cooling is taken out, and removes carbon, after the Ball milling, the after scouring that sieves, oven dry then, sieve and promptly obtain efficient blue emitting phophor, it is 104 that 147nm excites down luminosity.
Embodiment 2
Take by weighing BaCO
30.09 mole, Al
2O
30.5 mole, 0.1 mole of MgO, Eu
2O
30.005 mole, NH
40.015 mole of F, other condition is with embodiment 1, and the fluor that is obtained brightness under 147nm excites is 103.
Embodiment 3
Take by weighing BaC
2O
42H
20.08 mole of O, Al (OH)
31 mole, Mg (OH)
20.1 mole, Eu
2O
30.01 mole, H
3BO
30.002 mole, AlF
30.004 mole, other condition are with embodiment 1, the fluor that is obtained brightness under 147nm excites is 102.
Embodiment 4
Take by weighing BaCO
30.095 mole, BaC
2O
42H
20.01 mole of O, Al
2O
30.5 mole, 0.1 mole of MgO, Eu
2O
30.002 mole, H
3BO
30.003 mole, BaF
20.002 mole, other condition are with embodiment 1, the fluor that is obtained brightness under 147nm excites is 101.
Embodiment 5
Take by weighing 0.09 mole of BaO, Al
2O
30.5 mole, 0.09 mole of MgO, Mg (OH)
20.01 mole, Eu
2O
30.005 mole, H
3BO
30.005 mole, calcination temperature is 1400 ℃, and calcination is 8 hours, and other condition is with embodiment 1, and the fluor that is obtained brightness under 147nm excites is 103.
Embodiment 6
Take by weighing BaCO
30.09 mole, Al
2O
30.5 mole, 0.05 mole of MgO, (MgCO
3)
4Mg (OH)
25H
20.01 mole of O, Eu
2O
30.005 mole, MgF
20.006 mole, other condition are with embodiment 1, the fluor that is obtained brightness under 147nm excites is 105.
Embodiment 7
Take by weighing BaCO
30.09 mole, Al
2O
30.5 mole, (MgCO
3)
4Mg (OH)
25H
2The O0.02 mole, Eu
2O
30.005 mole, in 1400 ℃ of calcinations 3 hours, other condition was with embodiment 1, took out to grind, and then calcination 3 hours under 1600 ℃ of reducing atmospheres, and the fluor that is obtained excites down at 147nm that brightness is 108.
Embodiment 8
Take by weighing BaCO
30.09 mole, Al (OH)
31 mole, Mg (OH)
20.1 mole, Eu
2O
30.005 mole, utilize ball mill to carry out abundant ground and mixed, the mixture that is obtained is put into a less alumina crucible adds a cover, it is being put into bigger crucible then, add a cover after putting into carbon or graphite, put into High Temperature Furnaces Heating Apparatus, in 1700 ℃ of calcinations 2 hours, other condition is with embodiment 1, and the luminosity of gained fluor is 106.
Claims (1)
1. the preparation method of a vacuum ultraviolet rays activated blue aluminate fluorescent powder, the chemical formula of described fluor is:
Ba
1-xEu
xMgAl
10O
17，
0.04≤x≤0.2 wherein,
The starting material that adopt are: europium sesquioxide; Barium oxide maybe can transform one or both compounds in the barium carbonate of corresponding oxide or the barium oxalate; Magnesium oxide maybe can transform in magnesium hydroxide, magnesiumcarbonate or the magnesium oxalate of corresponding oxide one or more; Aluminum oxide is or/and can be converted into the aluminium hydroxide of corresponding oxide;
Fusing assistant be 0～6% mole of boric acid, Neutral ammonium fluoride, aluminum fluoride, magnesium fluoride or barium fluoride wherein one or more;
To put into graphite or carbon calcination between outer crucible and the interior crucible, calcination temperature is 1400～1700 ℃; Calcination time is 1～8 hour; Calcination 1-2 time; Cooling is taken out, and gets powdery phosphor through crushing screening, and 147nm excites down, and luminosity is greater than 100.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021553211A CN1189535C (en) | 2002-12-10 | 2002-12-10 | Method for preparing blue luminescent powder of aluminate activated by vacuum ultraviolet radiation |
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|---|---|---|---|
| CNB021553211A CN1189535C (en) | 2002-12-10 | 2002-12-10 | Method for preparing blue luminescent powder of aluminate activated by vacuum ultraviolet radiation |
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|---|---|
| CN1415695A CN1415695A (en) | 2003-05-07 |
| CN1189535C true CN1189535C (en) | 2005-02-16 |
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|---|---|---|---|
| CNB021553211A Expired - Fee Related CN1189535C (en) | 2002-12-10 | 2002-12-10 | Method for preparing blue luminescent powder of aluminate activated by vacuum ultraviolet radiation |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101353577A (en) * | 2007-07-23 | 2009-01-28 | 罗地亚（中国）投资有限公司 | Preparation of mixing oxide of yttrium and rare-earth elements |
| CN102212368B (en) * | 2010-04-02 | 2014-05-07 | 财团法人工业技术研究院 | Blue-light fluorescent material, white-light emitting device using same and solar battery |
| CN102277171B (en) * | 2011-09-09 | 2013-03-13 | 太原理工大学 | Method for preparing up-conversion white light fluorescent powder |
| CN106367067B (en) * | 2016-08-30 | 2019-05-17 | 内蒙古科技大学 | A kind of aluminate blue fluorescent powder and preparation method thereof |
| CN113831916B (en) * | 2021-10-11 | 2023-06-02 | 中国人民解放军陆军工程大学 | Preparation method of rare earth doped long afterglow luminescent material |
| CN114874769B (en) * | 2022-03-17 | 2024-02-27 | 宝鸡文理学院 | Preparation method of thermoluminescent color-changing fluorescent powder |
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2002
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