CN101701153B - Method for preparing aluminate green phosphor with low content of terbium - Google Patents
Method for preparing aluminate green phosphor with low content of terbium Download PDFInfo
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- CN101701153B CN101701153B CN2009103098778A CN200910309877A CN101701153B CN 101701153 B CN101701153 B CN 101701153B CN 2009103098778 A CN2009103098778 A CN 2009103098778A CN 200910309877 A CN200910309877 A CN 200910309877A CN 101701153 B CN101701153 B CN 101701153B
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Abstract
The invention discloses a method for preparing aluminate green phosphor with low content of terbium, which comprises the steps: preparing powder without terbium at first, precipitating Tb element on the powder and then putting the powder into high temperature reaction in the reducing atmosphere to obtain aluminate green phosphor with the component of CeaMgAl11O10:Tb1-a. The aluminate green phosphor prepared by the method has terbium content which can be lowered by 10-40% and relative brightness which is lowered by 1-5% only, therefore, the method effectively reduces production cost of terbium-excited aluminate green phosphor and raises price performance of the aluminate green phosphor.
Description
Technical field
The present invention relates to the preparation method of the aluminate green powder that a kind of terbium excites, particularly a kind of preparation method of aluminate green phosphor with low content of terbium.
Background technology
The chemical constitution of the aluminate green powder that terbium excites is Ce
aMgAl
110
19: Tb
1-a, (0.6≤a＜1) is one of green powder commonly used in the three-color fluorescent lamp, its best proportioning is Ce
0.67MgAl
11O
19: Tb
0.33The terbium element is the element that excites of this fluorescent material, is indispensable element in this green powder.
The synthetic basic high temperature solid-state method that adopts of existing aluminate green powder, rare earth ion is evenly distributed on the surperficial and inner of matrix, needs to use more terbium element like this.Costing an arm and a leg of rare-earth oxidation terbium makes to have holding at high price of many aluminate greens powder now, increased the cost of luminescent lamp.As reduce terbium content in many aluminate greens powder, and the price of green powder no doubt can descend to some extent, but same, and the light-emitting phosphor performance also can significantly reduce.People are seeking a kind of constant basically at the luminescent properties that keeps fluorescent material always, the method for low many aluminate greens of the terbium content powder of preparation.
Summary of the invention
The object of the present invention is to provide a kind of preparation method who keeps constant basically low many aluminate greens of the terbium content powder of aluminate green powder luminescent properties.
The technical scheme that the present invention taked is: a kind of preparation method of aluminate green phosphor with low content of terbium is characterized in that may further comprise the steps:
1) by the aluminate fluorescent powder that will prepare form, get the compound of the cerium that contains the corresponding mol ratio example, magnesium, aluminium, adopt the high temperature solid-state method sintering, grind the aluminate powder A that is not contained terbium;
2) by the aluminate fluorescent powder that will prepare form; Get the Tb solion that contains the corresponding mol ratio example; Under whipped state, powder A is poured in the Tb solion, regulate Tb solion pH value to solution with basic soln again and be alkalescence, make the surface of Tb ion precipitation at powder A;
3) the complete post precipitation of Tb ion with solution suction filtration, drying, obtains loose powder B;
4) powder B is put into crucible, go back under the atmosphere protection,, take out naturally cooling, grind and obtain title product at 1300-1600 ℃ of reductase 12-6 hour weak.
Preferably, the basic soln of adjusting pH value is the basic soln of non-metallic ion.
The invention has the beneficial effects as follows: by the aluminate green phosphor with low content of terbium of the inventive method preparation, the terbium element concentrates on the upper layer of powder, and powder inside does not have the terbium element basically; Greatly reduce the usage quantity of terbium element in the aluminate green powder like this; The realization data show that terbium content can reduce by 10 ~ 40%, but the luminescent properties of fluorescent material only reduces by 1 ~ 5%; Greatly reduce the cost of aluminate green powder, improved cost performance of product.
Description of drawings
Fig. 1 is the XRD figure of the embodiment of the invention 4;
Fig. 2 is the emmission spectrum figure of the embodiment of the invention 4 and Comparative Examples 1.
Embodiment
Below in conjunction with instance, further specify the present invention.
Embodiment 1
Ce
0.80MgAl
11O
19:Tb
0.20
1) gets cerium oxide 3.581g, Natural manganese dioxide 1.049g, aluminum oxide 14.582g, Sellaite 0.096g; In mortar, grind after one hour, put into crucible, calcining is after 7 hours in 1600 ℃ retort furnace; Naturally cooling takes out the back and grinds half hour, makes the powder A that does not contain the terbium element;
2) get terbium sesquioxide 0.972g, be dissolved in the hydrochloric acid, be made into the Tb solion of 0.05mol/L, powder A is poured in the Tb solion, under whipped state, slowly add the ammoniacal liquor of 2mol/L, the pH value is adjusted to 8.0, make the Tb ion precipitation on powder A surface;
3) continue then to stir 30 minutes, left standstill again 30 minutes, the Tb ion is precipitated fully, filter, dry, obtain loose powder B.
4) this powder is put into crucible, at N
295%/H
2, take out after naturally cooling to room temperature after 3 hours in reaction under 1450 ℃ the temperature in 5% the reducing atmosphere, grind and promptly obtain target fluorescent material after 10 minutes.
Embodiment 2:
Ce
0.78MgAl
11O
19:Tb
0.22
1) gets cerium oxide 3.490g, Natural manganese dioxide 1.048g, aluminum oxide 14.575g, boric acid 0.191g; In mortar, grind after one hour, put into crucible, calcining is after 6 hours in 1500 ℃ retort furnace; Naturally cooling takes out the back and grinds half hour, makes the powder A that does not contain the terbium element;
2) get terbium sesquioxide 1.069g, be dissolved in the hydrochloric acid, be made into the solution of 0.05mol/L, powder A is poured in the Tb solion, under whipped state, add the urea soln 25ml of 1mol/L, then solution is heated to 90 ℃, make the Tb ion precipitation on powder A surface;
3) constant temperature is 2 hours, continues then to stir 30 minutes, leaves standstill 30 minutes again, and the Tb ion is precipitated fully, filters, dries, and obtains loose powder B;
4) this powder B is put into crucible, at N
290%/H
2, take out after naturally cooling to room temperature after 4 hours in reaction under 1300 ℃ the temperature in 10% the reducing atmosphere, grind and promptly obtain target fluorescent material after 10 minutes.
Embodiment 3:
Ce
0.75MgAl
11O
19:Tb
0.25
1) gets cerium oxide 3.353g, Natural manganese dioxide 1.047g, aluminum oxide 14.565g, ALUMNIUM FLUORIDE 0.569g; In mortar, grind after one hour, put into crucible, calcining is after 5 hours in 1450 ℃ retort furnace; Naturally cooling takes out the back and grinds half hour, makes the powder A that does not contain the terbium element.
2) get terbium sesquioxide 1.214g, be dissolved in the nitric acid, be made into the Tb solion of 0.20mol/L, powder A is poured in the Tb solion, under whipped state, slowly add the ammoniacal liquor of 10mol/L, the pH value is adjusted to 9.5, make the Tb ion precipitation on powder A surface;
3) continue to stir 60 minutes, left standstill again 45 minutes, the Tb ion is precipitated fully, filter, dry, obtain loose powder B;
4) this powder is put into crucible, at N
295%/H
2, take out after naturally cooling to room temperature after 5 hours in reaction under 1525 ℃ the temperature in 5% the reducing atmosphere, grind and promptly obtain target fluorescent material after 10 minutes.
Embodiment 4:
Ce
0.70MgAl
11O
19:Tb
0.30
1) gets cerium oxide 3.126g, Natural manganese dioxide 1.046g, aluminum oxide 14.547g, strontium fluoride 0.281g; In mortar, grind after one hour, put into crucible, calcining is after 3 hours in 1400 ℃ retort furnace; Naturally cooling takes out the back and grinds half hour, makes the powder A that does not contain the terbium element;
2) get terbium sesquioxide 1.455g, be dissolved in the hydrochloric acid, be made into the Tb solion of 0.50mol/L, powder A is poured in the solution, under whipped state, slowly add the ammoniacal liquor of 1mol/L, the pH value is adjusted to 7.0, make the Tb ion precipitation on powder A surface;
3) continue to stir 120 minutes, left standstill again 120 minutes, the Tb ion is precipitated fully, filter, dry, obtain loose powder B;
4) powder B is put into crucible, in carbon reducing agent atmosphere, after 6 hours, take out after naturally cooling to room temperature, grind and promptly obtain target fluorescent material after 10 minutes in reaction under 1600 ℃ the temperature.
Embodiment 5:
Ce
0.73MgAl
11O
19:Tb
0.27
1) gets cerium oxide 3.262g, Natural manganese dioxide 1.047g, aluminum oxide 14.558g, lithium fluoride 0.377g; In mortar, grind after one hour, put into crucible, calcining is after 4 hours in 1400 ℃ retort furnace; Naturally cooling takes out the back and grinds half hour, makes the powder A that does not contain the terbium element;
2) get terbium sesquioxide 1.310g, be dissolved in the hydrochloric acid, be made into the Tb solion of 0.2mol/L, powder A is poured in the Tb solion, under whipped state, slowly add the ammoniacal liquor of 4mol/L, the pH value is adjusted to 8.5, make the Tb ion precipitation on powder A surface;
3) continue to stir 90 minutes, left standstill 90 minutes again, the Tb ion is precipitated fully, filter, oven dry obtains loose powder B;
4) powder B is put into crucible, at N
295%/H
2, take out after naturally cooling to room temperature after 5 hours in reaction under 1380 ℃ the temperature in 5% the reducing atmosphere, grind and promptly obtain target fluorescent material after 10 minutes.
Comparative Examples 1:
Ce
0.67MgAl
11O
19:Tb
0.33
Get cerium oxide 2.992g, Natural manganese dioxide 1.046g, aluminum oxide 14.548g; Terbium sesquioxide 1.061g, boric acid 0.202g grinds after one hour in mortar; Put into crucible, in 1500 ℃ retort furnace, calcine after 4 hours naturally cooling; Take out the back and grind half hour, then this powder is put into crucible, at N
295%/H
2, take out after naturally cooling to room temperature after 4 hours in reaction under 1300 ℃ the temperature in 5% the reducing atmosphere, grind and promptly obtain target fluorescent material after 10 minutes.
Comparative Examples 2:
Ce
0.83MgAl
11O
19:Tb
0.17
1) gets cerium oxide 3.718g, Natural manganese dioxide 1.049g, aluminum oxide 14.593g, Sellaite 0.202g; In mortar, grind after one hour, put into crucible, calcining is after 8 hours in 1500 ℃ retort furnace; Naturally cooling takes out the back and grinds half hour, makes the powder A that does not contain the terbium element;
2) get terbium sesquioxide 0.827g, be dissolved in the hydrochloric acid, be made into the terbium chloride solution of 0.10mol/L, powder A is poured in the solution, under whipped state, slowly add the ammoniacal liquor of 5mol/L, the pH value is adjusted to 9.0, make the Tb ion precipitation on powder A surface;
3) continue to stir 30 minutes, left standstill 30 minutes again, the Tb ion is precipitated fully, filter, oven dry obtains loose powder B;
4) powder B is put into crucible, at N
295%/H
2, take out after naturally cooling to room temperature after 2 hours in reaction under 1300 ℃ the temperature in 5% the reducing atmosphere, grind and promptly obtain target fluorescent material after 10 minutes.
In view of the fusing assistant that uses is the fusing assistant commonly used of this area, only enumerate wherein 5 kinds in the embodiment of the invention, but this and do not mean that and can only use this 5 kinds of fusing assistants.
Fig. 1 is the XRD figure of the embodiment of the invention 4, is characterized by the aluminate green powder that terbium excites.
Fig. 2 is the emmission spectrum figure of the embodiment of the invention 4 and Comparative Examples 1, and among the figure, that solid line is represented is the emmission spectrum figure of Comparative Examples 1, and that dotted line is represented is the emmission spectrum figure of embodiment 4, and both differences are very little.
It is to excite under the ultraviolet ray of 254nm at wavelength that above-mentioned each terbium excites the aluminate green powder, records its luminosity, experimental data such as table 1.
Table 1: the terbium element uses reduction amount luminescent properties change list
| Numbering | The terbium element uses reduction amount/% | Relative brightness |
| Comparative Examples 1 | 0 | 100 |
| Embodiment 1 | 39.4 | 94.7 |
| |
33.3 | 96.1 |
| Embodiment 3 | 24.2 | 97.4 |
| Embodiment 4 | 9.1 | 98.7 |
| Embodiment 5 | 18.2 | 98.0 |
| Comparative Examples 2 | 48.5 | 88.5 |
Can be known that by above data analysis the usage quantity of terbium element reduces 40% when following than ordinary method among the present invention, the luminescent properties of fluorescent material does not have great variation, has only reduced less than 5%; After the minimizing of terbium element usage quantity surpassed 40%, the light-emitting phosphor performance had reduction largely, is unfavorable for commercialization.So among the present invention, the use reduction of terbium element should be below 40%.
Claims (7)
1. the preparation method of an aluminate green phosphor with low content of terbium is characterized in that may further comprise the steps:
1) by the aluminate fluorescent powder that will prepare form, get the compound of the cerium that contains the corresponding mol ratio example, magnesium, aluminium, adopt the high temperature solid-state method sintering, grind the aluminate powder A that is not contained terbium;
2) by the aluminate fluorescent powder that will prepare form; Get the Tb solion that contains the corresponding mol ratio example; Under whipped state, powder A is poured in the Tb solion, regulate Tb solion pH value to solution with basic soln again and be alkalescence, make the surface of Tb ion precipitation at powder A;
3) the complete post precipitation of Tb ion with solution suction filtration, drying, obtains loose powder B;
4) powder B is put into crucible, go back under the atmosphere protection,, take out naturally cooling, grind and obtain title product at 1300-1600 ℃ of reductase 12-6 hour weak;
Wherein, said Tb solion is water-soluble terbium salts solution.
2. the preparation method of a kind of aluminate green phosphor with low content of terbium according to claim 1 is characterized in that: in preparation powder A, add fusing assistant.
3. the preparation method of a kind of aluminate green phosphor with low content of terbium according to claim 2 is characterized in that: the fusing assistant usage quantity is 0.5～3% of the solid material gross weight of preparation powder A.
4. the preparation method of a kind of aluminate green phosphor with low content of terbium according to claim 2, it is characterized in that: fusing assistant is MgF
2, BaF
2, AlF
3, SrF
2, H
3BO
3, LiF.
5. the preparation method of a kind of aluminate green phosphor with low content of terbium according to claim 1, it is characterized in that: water-soluble terbium salt is terbium chloride, Terbium trinitrate.
6. the preparation method of a kind of aluminate green phosphor with low content of terbium according to claim 1 is characterized in that: the basic soln of regulating the pH value is the basic soln of non-metallic ion.
7. the preparation method of a kind of aluminate green phosphor with low content of terbium according to claim 1, it is characterized in that: the basic soln of said non-metallic ion is ammoniacal liquor, urea soln.
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| WO2011134165A1 (en) * | 2010-04-30 | 2011-11-03 | 海洋王照明科技股份有限公司 | Aluminate fluorescent materials and preparation methods thereof |
| CN102373060B (en) * | 2011-10-19 | 2013-06-12 | 江门市科恒实业股份有限公司 | Aluminate green fluorescent powder with core-shell structure and preparation method thereof |
| CN102888224A (en) * | 2012-09-07 | 2013-01-23 | 彩虹集团电子股份有限公司 | Method for preparing ultraviolet excited or vacuum ultraviolet excited green emitting phosphor |
| CN103102879B (en) * | 2013-02-28 | 2015-05-20 | 福建省长汀金龙稀土有限公司 | Method for preparing CAT green phosphor for once-firing lamp |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1118802A (en) * | 1993-01-11 | 1996-03-20 | 余宪恩 | Green powder, blue powder of aluminosilicate and its three primary colour fluorescent powder series |
| US5989454A (en) * | 1998-07-06 | 1999-11-23 | Matsushita Electric Industrial Co., Ltd. | Method for making small particle blue emitting lanthanum phosphate based phosphors |
| US20030122108A1 (en) * | 2001-10-31 | 2003-07-03 | Ravilisetty Padmanabha Rao | Method of making blue emitting aluminate phosphor for VUV excited light emitting device |
| CN101402854A (en) * | 2008-11-05 | 2009-04-08 | 江门市科恒实业股份有限公司 | Coating material applied to improve thermostability of lanthanum-cerium-terbium phosphate green emitting phosphor and method of producing the same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1118802A (en) * | 1993-01-11 | 1996-03-20 | 余宪恩 | Green powder, blue powder of aluminosilicate and its three primary colour fluorescent powder series |
| US5989454A (en) * | 1998-07-06 | 1999-11-23 | Matsushita Electric Industrial Co., Ltd. | Method for making small particle blue emitting lanthanum phosphate based phosphors |
| US20030122108A1 (en) * | 2001-10-31 | 2003-07-03 | Ravilisetty Padmanabha Rao | Method of making blue emitting aluminate phosphor for VUV excited light emitting device |
| CN101402854A (en) * | 2008-11-05 | 2009-04-08 | 江门市科恒实业股份有限公司 | Coating material applied to improve thermostability of lanthanum-cerium-terbium phosphate green emitting phosphor and method of producing the same |
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