CN1366017A - Vacuum ultraviolet ray excited green barium magnesium aluminate as fluorescent substance and its preparing process - Google Patents

Vacuum ultraviolet ray excited green barium magnesium aluminate as fluorescent substance and its preparing process Download PDF

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Publication number
CN1366017A
CN1366017A CN 02104175 CN02104175A CN1366017A CN 1366017 A CN1366017 A CN 1366017A CN 02104175 CN02104175 CN 02104175 CN 02104175 A CN02104175 A CN 02104175A CN 1366017 A CN1366017 A CN 1366017A
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gram
vacuum ultraviolet
fluorescent substance
magnesium aluminate
excited
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尤洪鹏
吴雪艳
洪广言
崔洪涛
吴琼
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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Abstract

An efficient fluoresence body stimulated by vacuum ultraviolet ray is a Mn-activated barium magnesium aluminate, its chemical composition being BaMg1-xMnxAlyO2+1.5y, where x=0.06-0.3, and y=9.5-12. Its preparing process includes such steps as choosing raw materials containing Al, Ba, Mg and Mn sources, mixing with flux, calcining at 1350-1700 deg.C for 1-10 hr in the reducing atmosphere generated by burning carbon or graphite in air, and cooling. It can be used for display and lighting elements.

Description

Green barium magnesium aluminate as fluorescent substance of excited by vacuum ultraviolet and preparation method thereof
Technical field: the present invention relates to efficient barium magnesium aluminate as fluorescent substance of a kind of manganese ion doping and preparation method thereof.This high-efficiency fluorescence body excites the green emitting that has down at vacuum ultraviolet rays, and it can be used for demonstration and illuminating devices such as large color screen plasma panel display and rare gas lamp.
Background technology: in recent years, vacuum ultraviolet rays excites down the more and more important of high efficient luminous material change, it one of is mainly used is large color screen high-definition plasma body flat-panel monitor (PDP), PDP utilizes Xe, Ne-Xe, thereby the light that the vacuum ultraviolet rays that noble gas discharges such as Ar produce excites different fluor to produce three kinds of distinct colors of red, green, blue obtains color picture.Vacuum ultraviolet rays excites down the quality of fluor directly to determine the quality of color picture and the life-span of device, and therefore, its fluor is the important component part of PDP, and it plays an important role.The vacuum ultraviolet-excited Another application field of high-efficiency fluorescence body down is to make non-mercury florescent lamp.Used luminescent lamp mostly excites with the mercury ionizing ray at present, in the process of producing and using, can cause environmental pollution, for this reason, people are developing and are utilizing Xe, Ne-Xe, the vacuum ultraviolet rays excited fluorescent lamp that noble gas discharges such as Ar produce, this luminescent lamp utilizes the noble gas discharge excited fluophor of environmentally safe and does not need mercury, is non-mercury florescent lamp therefore.
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 fluor remain in some shortcomings under vacuum ultraviolet rays excites, as, the rouge and powder purity of color is relatively poor, and green powder fluorescence lifetime is long, the blue powder less stable.Simultaneously, the efficient of these luminescent materials still has the leeway of raising.Therefore, await developing the luminescent material that new and effective vacuum ultraviolet rays excites.
Green-emitting phosphor is the important component part of three-color light-emitting material because vacuum ultraviolet rays excites down efficiently, therefore, develops the significant of new and effective green-emitting phosphor.Therefore people are carrying out number of research projects aspect the new and effective green-emitting phosphor of development, and constantly have patent open in succession, as, United States Patent (USP) 5725800 discloses a kind of vacuum ultraviolet-excited efficient green fluor down, they consist of La 1-a-bTb aCe bPO 4Although it has higher luminous efficiency, its purity of color is not as doped with Mn 2+The ionic fluor.And for example U.S. Pat 5868963 discloses a kind of vacuum ultraviolet-excited efficient green fluor Ba down 2Al 12-xMn xO 18-0.5x+zThe preparation method, exciting at vacuum ultraviolet rays of this fluor has down higher luminous efficiency.
Summary of the invention: an object of the present invention is to provide the green-emitting phosphor that a kind of vacuum ultraviolet rays efficiently excites; Another purpose provides a kind of preparation method of the excited fluorescent of vacuum ultraviolet rays efficiently body.
Fluor of the present invention is that bivalent manganese activates barium magnesium aluminate, its structure is the beta-alumina structure, divalent manganesetion replaces the case of the magnesium ion of four-coordination in barium magnesium aluminate, under the vacuum-ultraviolet light irradiation, the matrix absorption vacuum-ultraviolet light also passes to divalent manganesetion to luminous energy, the electronics of mn 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 green glow.Because mn ion is easy to oxidation in air, the formation of barium magnesium aluminate needs reaction at high temperature, so its preparation will be carried out in high temperature reduction atmosphere.
The high-efficiency fluorescence body that the vacuum ultraviolet rays that the present invention proposes excites is manganese activated barium magnesium aluminate, and its chemical constitution formula is:
BaMg 1-XMn XAl YO 2+1.5Y
Wherein X and Y are: 0.06≤X≤0.30; 9.5≤Y≤12
The starting material that adopted are: manganous carbonate, manganous sulfate, manganous oxalate be one or more compounds wherein; Barium carbonate, hydrated barta, barium oxalate be one or more compounds wherein; Magnesium oxide, magnesiumcarbonate, magnesium hydroxide be one or more compounds wherein; Aluminum oxide, aluminium hydroxide is one or more compounds wherein.
Fusing assistant is 0～4% mole of aluminum fluoride, magnesium fluoride, barium fluoride, Neutral ammonium fluoride, boric acid, bariumchloride wherein one or more.
The reducing gas that reaction atmosphere burns in air and produces with carbon or graphite, or be 1～5%H with volume ratio 2With 99～95%N 2Mixed gas.
Carry out calcination in high temperature reduction atmosphere, calcination temperature is 1350～1700 ℃, and calcination time is 1～10 hour, and cooling is taken out, and promptly gets required high-efficiency fluorescence body through crushing screening.
Preparation technology of the present invention is simple, and easy handling, the green-emitting phosphor of preparing its luminous intensity under the 147nm vacuum ultraviolet rays excites is higher than BaAl 12O 19, Mn.The fluorescence physical efficiency of preparing is satisfied with the application of demonstrations such as large color screen plasma panel display and rare gas lamp and illuminating device better.
Embodiment is as follows:
Embodiment 1
Take by weighing Al 2O 372.64 gram, MgO 4.84 grams, BaCO 329.60 gram, MnCO 33.45 gram, MgF 20.28 gram utilizes ball mill to carry out abundant ground and mixed, puts into alumina crucible, in starting material, cover one deck carbon or graphite, build crucible cover, put into High Temperature Furnaces Heating Apparatus, 1450 ℃, calcination 5 hours is taken out behind the naturally cooling, remove carbon, after adding entry and pellet shot from a slingshot Ball milling, the after scouring that sieves, oven dry then, sieve and promptly obtain the efficient green fluor, its luminosity is 108 (with BaAl 12O 19: 0.2Mn).
Embodiment 2
Take by weighing Al 2O 376.47 gram, MgO 4.84 grams, BaCO 329.60 gram, MnCO 33.45 gram, H 3BO 30.28 gram, other condition are with example 1, the fluor that is obtained brightness under 147nm excites is 110.
Embodiment 3
Take by weighing Al 2O 380.29 gram, MgO 4.84 grams, BaCO 329.60 gram, MnCO 33.45 gram, NH 4F 0.18 gram, other condition are with example 1, and the fluor that is obtained brightness under 147nm excites is 112.
Embodiment 4
Take by weighing Al 2O 384.12 gram, MgO 4.84 grams, BaCO 329.60 gram, MnCO 33.45 gram, MgF 20.18 gram, NH 4F 0.1 gram, other condition are with example 1, and the fluor that is obtained brightness under 147nm excites is 112.
Embodiment 5
Take by weighing Al 2O 387.94 gram, MgO 4.84 grams, BaCO 329.60 gram, MnCO 33.45 gram, BaCl 22H 2O 0.64 gram, other condition are with example 1, and the fluor that is obtained brightness under 147nm excites is 108.
Embodiment 6
Take by weighing Al 2O 391.76 gram, MgO 4.84 grams, BaCO 329.60 gram, MnCO 33.45 gram, MgF 20.28 gram, BaCl 22H 2O 0.10 gram, other condition are with example 1, and the fluor that is obtained brightness under 147nm excites is 106.
Embodiment 7
Take by weighing Al 2O 384.12 gram, MgO 5.68 grams, BaCO 329.60 gram, MnCO 31.03 gram, BaF 20.53 gram, other condition are with example 1, the fluor that is obtained brightness under 147nm excites is 104.
Embodiment 8
Take by weighing Al 2O 384.12 gram, BaCO 329.60 gram, (MgCO 3) 4Mg (OH) 25H 2O 9.71 grams, MnCO 33.45 gram, MgF 20.28 1450 ℃ of calcinations are 4 hours under the reducing atmosphere of nitrogen and hydrogen (hydrogen that contains 2% volume), other condition is with example 1, and the fluor that is obtained excites down at 147nm that brightness is 108.
Embodiment 9
Take by weighing Al 2O 384.12 gram, Mg (OH) 26.12 gram, BaCO 329.60 gram, MnCO 35.17 gram, AlF 30.35 gram, utilize ball mill to carry out abundant ground and mixed, the mixture that is obtained is put into alumina crucible, under the reducing atmosphere of nitrogen and hydrogen (hydrogen that contains 1% volume), 3 hours other conditions of 1450 ℃ of calcinations are with example 1, and the fluor that is obtained brightness under 147nm excites is 103.
Embodiment 10
Take by weighing Al 2O 384.12 gram, MgO 2.66 grams, Mg (OH) 23.84 gram, BaCO 329.60 gram, MnCO 32.07 gram, AlF 30.5 gram utilizes ball mill to carry out abundant ground and mixed, and the mixture that is obtained is put into alumina crucible, under the reducing atmosphere of nitrogen and hydrogen (hydrogen that contains 5% volume), 1350 ℃ of calcinations 10 hours, other condition is with example 1, and the luminosity of gained fluor is 110.
Take by weighing Al 2O 384.12 gram, MgO 4.84 grams, BaCO 329.60 gram, MnCO 33.45 gram, MgF 20.18 gram, NH 4F 0.1 gram, other condition are with example 1, and the fluor that is obtained brightness under 147nm excites is 112.
Embodiment 5
Take by weighing Al 2O 387.94 gram, MgO 4.84 grams, BaCO 329.60 gram, MnCO 33.45 gram, BaCl 22H 2O 0.64 gram, other condition are with example 1, and the fluor that is obtained brightness under 147nm excites is 108.
Embodiment 6
Take by weighing Al 2O 391.76 gram, MgO 4.84 grams, BaCO 329.60 gram, MnCO 33.45 gram, MgF 20.28 gram, BaCl 22H 2O 0.10 gram, other condition are with example 1, and the fluor that is obtained brightness under 147nm excites is 106.
Embodiment 7
Take by weighing Al 2O 384.12 gram, MgO 5.68 grams, BaCO 329.60 gram, MnCO 31.03 gram, BaF 20.53 gram, other condition are with example 1, the fluor that is obtained brightness under 147nm excites is 104.
Embodiment 8
Take by weighing Al 2O 384.12 gram, BaCO 329.60 gram, (MgCO 3) 4Mg (OH) 25H 2O 9.71 grams, MnCO 33.45 gram, MgF 20.28 1450 ℃ of calcinations are 4 hours under the reducing atmosphere of nitrogen and hydrogen (hydrogen that contains 2% volume), other condition is with example 1, and the fluor that is obtained excites down at 147nm that brightness is 108.
Embodiment 9
Take by weighing Al 2O 384.12 gram, Mg (OH) 26.12 gram, BaCO 329.60 gram, MnCO 35.17 gram, AlF 30.35 gram, utilize ball mill to carry out abundant ground and mixed, the mixture that is obtained is put into alumina crucible, under the reducing atmosphere of nitrogen and hydrogen (hydrogen that contains 1% volume), 3 hours other conditions of 1450 ℃ of calcinations are with example 1, and the fluor that is obtained brightness under 147nm excites is 103.
Embodiment 10
Take by weighing Al 2O 384.12 gram, MgO 2.66 grams, Mg (OH) 23.84 gram, BaCO 329.60 gram, MnCO 32.07 gram, AlF 30.5 gram utilizes ball mill to carry out abundant ground and mixed, and the mixture that is obtained is put into alumina crucible, under the reducing atmosphere of nitrogen and hydrogen (hydrogen that contains 5% volume), 1350 ℃ of calcinations 10 hours, other condition is with example 1, and the luminosity of gained fluor is 110.
Embodiment 11
Take by weighing Al 2O 384.12 gram, MgO 5.32 grams, BaCO 323.68 gram, Ba (OH) 25.14 gram .MnC 2O 42H 2O 3.15 grams, temperature of reaction is 1700 ℃ of calcinations 1 hour, and other condition is with example 1, and the fluor that is obtained brightness under 147nm excites is 108.
Embodiment 12
Take by weighing Al 2O 384.12 gram, Al (OH) 3: 12.87 grams, MgO 1.59 grams, Mg (OH) 23.85 gram, (MgCO 3) 4Mg (OH) 25H 2O 2.14 grams, BaCO 329.60 gram, MnSO 4.H 2O 3.04 grams, AlF 30.5 gram, other condition is with example 1, and the luminosity of gained fluor is 110.

Claims (5)

1. the green barium magnesium aluminate as fluorescent substance of an excited by vacuum ultraviolet is characterized in that chemical constitution formula is:
BaMg 1-XMn XAl YO 2+1.5Y
Wherein: 0.06≤X≤0.30 9.5≤Y≤12
2. the preparation method of the green barium magnesium aluminate as fluorescent substance of an excited by vacuum ultraviolet, it is characterized in that the starting material that adopt are: manganous carbonate, manganous sulfate, manganous oxalate be one or more compounds wherein; Barium carbonate, hydrated barta, barium oxalate be one or more compounds wherein; Magnesium oxide, magnesiumcarbonate, magnesium hydroxide be one or more compounds wherein; Aluminum oxide, aluminium hydroxide is one or more compounds wherein;
Fusing assistant is 0～4% mole of aluminum fluoride, magnesium fluoride, barium fluoride, Neutral ammonium fluoride, boric acid, bariumchloride wherein one or more;
The reducing gas that reaction atmosphere burns in air and produces with carbon or graphite, or be 1～5%H with volume ratio 2With 99～95%N 2Mixed gas;
Carry out calcination in high temperature reduction atmosphere, calcination temperature is 1350～1700 ℃, and calcination time is 1～10 hour, and cooling is taken out, and promptly gets required high-efficiency fluorescence body through crushing screening.
3. the preparation method of the green barium magnesium aluminate as fluorescent substance of excited by vacuum ultraviolet as claimed in claim 2 is characterized in that the reducing gas that reaction atmosphere burns and produces with carbon in air.
4. the preparation method of the green barium magnesium aluminate as fluorescent substance of excited by vacuum ultraviolet as claimed in claim 2 is characterized in that the reducing gas that reaction atmosphere burns and produces with graphite in air.
5. the preparation method of the green barium magnesium aluminate as fluorescent substance of excited by vacuum ultraviolet as claimed in claim 2 is characterized in that the reaction atmosphere volume ratio is 1～5%H 2With 99～95%N 2Mixed gas.
CN 02104175 2002-03-15 2002-03-15 Vacuum ultraviolet ray excited green barium magnesium aluminate as fluorescent substance and its preparing process Pending CN1366017A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1306005C (en) * 2004-11-15 2007-03-21 王兵 Aluminate-base rare earth long afterglow luminous material synthesizing method
CN101130691B (en) * 2007-08-03 2010-06-09 西安理工大学 Method for improving luminous intensity of vacuum ultraviolet luminescent material with beta-Al2O3 structure
CN102280356A (en) * 2011-05-25 2011-12-14 扬州虹扬光电有限公司 Fluorescence glow lamp emitting blue light
CN101372345B (en) * 2007-08-21 2012-03-21 宇部材料工业株式会社 Method for producing fluorine-containing magnesium oxide fired product powder
CN102732250A (en) * 2012-06-27 2012-10-17 华南理工大学 Red phosphor and preparation method thereof
CN105331365A (en) * 2015-11-25 2016-02-17 浙江阳光美加照明有限公司 Preparation method of LED fluorescent powder
CN112266788A (en) * 2020-11-12 2021-01-26 厦门大学 Wide-spectrum near-infrared fluorescent material, near-infrared fluorescent glass, preparation method and device
CN114874769A (en) * 2022-03-17 2022-08-09 宝鸡文理学院 Preparation method of thermoluminescent color-changing fluorescent powder

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1306005C (en) * 2004-11-15 2007-03-21 王兵 Aluminate-base rare earth long afterglow luminous material synthesizing method
CN101130691B (en) * 2007-08-03 2010-06-09 西安理工大学 Method for improving luminous intensity of vacuum ultraviolet luminescent material with beta-Al2O3 structure
CN101372345B (en) * 2007-08-21 2012-03-21 宇部材料工业株式会社 Method for producing fluorine-containing magnesium oxide fired product powder
CN102280356A (en) * 2011-05-25 2011-12-14 扬州虹扬光电有限公司 Fluorescence glow lamp emitting blue light
CN102732250A (en) * 2012-06-27 2012-10-17 华南理工大学 Red phosphor and preparation method thereof
CN105331365A (en) * 2015-11-25 2016-02-17 浙江阳光美加照明有限公司 Preparation method of LED fluorescent powder
CN105331365B (en) * 2015-11-25 2017-08-29 浙江阳光美加照明有限公司 A kind of preparation method of LED fluorescent powder
CN112266788A (en) * 2020-11-12 2021-01-26 厦门大学 Wide-spectrum near-infrared fluorescent material, near-infrared fluorescent glass, preparation method and device
CN112266788B (en) * 2020-11-12 2021-12-17 厦门大学 Wide-spectrum near-infrared fluorescent material, near-infrared fluorescent glass, preparation method and device
CN114874769A (en) * 2022-03-17 2022-08-09 宝鸡文理学院 Preparation method of thermoluminescent color-changing fluorescent powder
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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