CN103571462A - Rare earth silicate orange-red fluorescent material for high-color-rendering energy saving lamp and preparation method - Google Patents
Rare earth silicate orange-red fluorescent material for high-color-rendering energy saving lamp and preparation method Download PDFInfo
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- CN103571462A CN103571462A CN201310541060.XA CN201310541060A CN103571462A CN 103571462 A CN103571462 A CN 103571462A CN 201310541060 A CN201310541060 A CN 201310541060A CN 103571462 A CN103571462 A CN 103571462A
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- rare earth
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Abstract
The invention relates to a rare earth silicate orange-red fluorescent material for a high-color-rendering energy saving lamp and a preparation method, aiming to obtain a rare earth fluorescent material for the energy saving lamp with high color rendering index by adopting the method and material provided by the invention. The general formula of the rare earth silicate orange-red fluorescent material for the high-color-rendering energy saving lamp is M<x-a>SiO5:aRe, wherein M is one or a composition of more than one of Ca, Sr and Ba; Re is one or a composition of more than one of Ce, Eu, Dy, Ho, Er, Tm and Yb; x is equal to 0-3; a is equal to 0-0.3. The preparation method comprises the following steps: weighing an oxide or a carbonate as a raw material M, a rare earth oxide and boric acid as a fluxing agent according to the stoichiometric ratio in the general formula M<x-a>SiO5:aRe, grinding the materials and mixing the powder uniformly, then putting the mixture in a high temperature furnace and carrying out firing once or more than once for 3-6 hours under the reducing atmosphere, thus obtaining the rare earth silicate orange-red fluorescent material for the high-color-rendering energy saving lamp.
Description
Technical field
The present invention relates to a class silicate luminescent material, it can be excited effectively in 250-500nm scope, and sends orange-ruddiness characteristic; It is mixed with rare earth luminescent material with trichromatic energy saving lamp, can obtain used for high color rendering property energy-saving lamp rare-earth luminescent material.
Background technology
Rare-earth trichromatic energy saving lamp still occupies sizable ratio in present illumination, and colour rendering index is an important indicator of electricity-saving lamp, rare-earth trichromatic fluorescent material (rouge and powder (Y
2o
3: Eu
3+), green powder (CeTbMgAl
11o
19), blue powder (BaMgAl
10o
17: Eu
2+) narrow-band spectrum, the discontinuity of the emmission spectrum of this electricity-saving lamp has determined by the colour temperature of its making that at the colour rendering index of 2300-8000K electricity-saving lamp, generally in 80 left and right, the deficiency that therefore will make up three primary colours line spectrum wave band could improve into the colour rendering index after lamp.
Limitation after rare-earth trichromatic fluorescent powder lamp processed determines to supplement the fluorescent material of certain wave band separately, could improve the colour rendering index of lamp.Therefore can analyze spectrogram and study for foundation, how improving Ra is to see in spectrum to lack which wave band, then synthesizes the fluorescent material with rock steady structure of these wave bands.Through research, show: the spectrum that is increased in 520~630nm can obviously improve the colour rendering index of electricity-saving lamp.Therefore, seeking the suitable fluorescent material of emmission spectrum within the scope of this is an important channel of improving color developing.
The research of silicate fluorescent material relatively early, is a class fluor that obtains the earliest application, as Mn
2+the zinc silicate and the beryllium zinc silicate that activate are the green-emitting phosphors that is used as the earliest luminescent lamp and CRT monitor.Alkaline-earth silicate is the efficient substrate material of supporting rare earth luminescence, has the features such as good stability, emmission spectrum wide coverage, is the focus system of the rare-earth luminescent material research of various ranges of application always.
Summary of the invention
The object of this invention is to provide by the light of 250-410nm and effectively excite, launch silicate fluorescent material and the preparation method of orange-ruddiness, by itself and rare-earth trichromatic fluorescent material rouge and powder (Y
2o
3: Eu
3+), green powder (CeTbMgAl
11o
19), blue powder (BaMgAl
10o
17: Eu
2+) fluorescent material mixing, can obtain the electricity-saving lamp rare-earth luminescent material that colour rendering index is high.
Technical scheme provided by the invention is: used for high-color developing energy-saving lamp rare earth silicate orange-red light flourescent material, the general formula that it is characterized in that this fluorescent material is M
x-asiO
5: aRe, wherein M is one or more the combination in Ca or Sr or Ba, Re is one or more the combination in Ce, Eu, Dy, Ho, Er, Tm or Yb, x=0-3; A=0-0.3.
In this fluorescent material, also add the boric acid of thousandth to thousand/ten mass ratio.
The preparation method of used for high-color developing energy-saving lamp rare earth silicate orange-red light flourescent material, the steps include: the oxide compound as raw material M or carbonate, and rare earth oxide and as the boric acid of fusing assistant, according to formula M
x-asiO
5: the stoichiometric ratio in aRe weighs up, and after being ground, puts into corundum crucible, in High Temperature Furnaces Heating Apparatus 1200-1400 ℃ temperature range, under reducing atmosphere, through the calcination of above 3-6 hour once or once, obtains.
Described reducing atmosphere is nitrogen hydrogen mixeding gas, density of hydrogen 1-12%.
The fineness of described fluorescent material is less than 10um.
The invention has the beneficial effects as follows: by adjusting the ratio of M ion and rare earth, can obtain launching main peak at the broadband spectral fluorescent material at 560-620nm place, can also effectively absorb 254 in electricity-saving lamp, 365,403 and the mercury line of 435nm, this has good effect to improving colour rendering index of electricity-saving lamp.Thereby by its with rare-earth trichromatic fluorescent material by different ratios mix obtain high-color rendering rare-earth luminescent material for electricity-saving lamp (generally lamp processed is aobvious refers to 80 for common rare-earth trichromatic fluorescence, add this type of silicate orange-red light flourescent material colour rendering index can be increased to 88 or more than).And what this class fluorescent material adopted is all to take silicate substrate as host lattice, and material has good stability, thereby the electricity-saving lamp obtaining also has satisfactory stability and consistence.
Accompanying drawing explanation
Fig. 1 is emmission spectrum of the present invention and excitation spectrum schematic diagram.
Embodiment
Fluorescent material in the present invention obtains by high temperature solid state reaction; Be about to oxide compound or carbonate as the M of raw material, silicon-dioxide and rare earth oxide, and the boric acid of a small amount of (thousandth to thousand of total mass/ten) is as fusing assistant, according to the stoichiometric ratio in accompanying drawing, weigh up, after being ground, put into corundum crucible, in High Temperature Furnaces Heating Apparatus 1200-1400 ℃ temperature range, under reducing atmosphere, through the calcination of above, 3-6 hour once or once, obtain.After the fluorescent material ball mill pulverizing obtaining by aforesaid method, obtain fluorescent material used in the present invention.
In accompanying drawing 1, can find out that as stated above the fluorescent material that obtains effectively exciting within the scope of 250-500nm is very clear, they can be by the optical excitation of this wavelength region, launch orange-ruddiness, so this fluorescent material is applicable to make up the spectrum of trichromatic energy saving lamp.
Below in conjunction with embodiment further explain used for high-color developing energy-saving lamp fluorescent material in the present invention preparation, the following examples only, for explanation, should not form the restriction to the scope of protection of present invention.
Fluorescent material Sr
2.90siO
5: 0.05Eu
2+, 0.05Er
3+preparation:
Take raw material
SrCO
3:4.2813g
SiO
2:0.6008g
Eu
2O
3:0.088g
Er
2O
3:0.0956g
H
3BO
3:0.0323g
After mixture material is ground and mixed, in 1250 ± 20 ℃ of temperature ranges of High Temperature Furnaces Heating Apparatus, a calcination through 4.5 hours under reducing atmosphere (nitrogen hydrogen mixeding gas, density of hydrogen 3-7%) obtains.The fluorescent material ball mill pulverizing obtaining by aforesaid method to fineness is to obtain fluorescent material used in the present invention after 8-9um.Its excitation spectrum and emmission spectrum are as shown in Figure 1.
Fluorescent material Sr
2.93eu
0.01ce
0.03siO
5: 0.03NaF Sr
2.93siO
5: 0.03Eu
2+, 0.04Dy
3+preparation:
Take raw material
SrCO
3:4.3256g
SiO
2:0.6008g
Eu
2O
3:0.0528g
Dy
2O
3:0.0746g
H
3BO
3:0.0329g
After mixture material is ground and is mixed, in 1300 ± 20 ℃ of temperature ranges of High Temperature Furnaces Heating Apparatus, reducing atmosphere (nitrogen hydrogen mixeding gas, density of hydrogen 6-10%) under, through twice calcination, obtain, calcination for the first time 3 hours, in room temperature cooling 1 hour, calcination for the second time 2 hours.The fluorescent material ball mill pulverizing obtaining by aforesaid method to fineness is to obtain fluorescent material used in the present invention after 5-7um.Its excitation spectrum and emmission spectrum are as shown in Figure 1.
Lamp embodiment processed
With aforesaid method, make fluorescent material (M
3siO
5: aRe) mix by certain mass ratio with trichromatic rare-earth luminescent material: orange red powder M
3siO
5: aRe(5-20%), rouge and powder Y
2o
3: Eu
3+(10-30%), green powder CeTbMgAl
11o
19(15-35%), blue powder BaMgAl
10o
17: Eu
2+(15-25%) can make more than 88 electricity-saving lamp of colour rendering index.
Numbering | Light efficiency | Coordinate | Colour temperature | Aobvious finger | Granularity/distribution | Powder kind ratio |
YOX:CAT:BAM | 70.2 | 0.3136/0.3439 | 6583K | 81.2 | 5.89/0.638 | 41:36:23 |
YOX:CAT:BAM:M 3SiO 5:aRe | 68.5 | 0.3143/0.3452 | 65132K | 88.2 | 5.84/0.654 | 28:35:25:12 |
YOX:CAT:BAM:M 3SiO 5:aRe | 68.1 | 0.3149/0.3444 | 65012K | 88.5 | 5.84/0.654 | 27:35:24:14 |
In table: YOX is rouge and powder, CAT is green powder, and BAM is blue powder;
M
3siO
5: aRe is the present invention (Sr
2.90siO
5: 0.05Eu
2+, 0.05Er
3+with Sr
2.93eu
0.01ce
0.03siO
5: 0.03NaF Sr
2.93siO
5: 0.03Eu
2+, 0.04Dy
3+be 1: 1 proportioning).
Claims (5)
1. used for high-color developing energy-saving lamp rare earth silicate orange-red light flourescent material, the general formula that it is characterized in that this fluorescent material is M
x-asiO
5: aRe, wherein M is one or more the combination in Ca or Sr or Ba, Re is one or more the combination in Ce, Eu, Dy, Ho, Er, Tm or Yb, x=0-3; A=0-0.3.
2. used for high-color developing energy-saving lamp rare earth silicate orange-red light flourescent material according to claim 1, is characterized in that: the boric acid that also adds thousandth to thousand/ten mass ratio in this fluorescent material.
3. the preparation method of used for high-color developing energy-saving lamp rare earth silicate orange-red light flourescent material, the steps include: the oxide compound as raw material M or carbonate, and rare earth oxide and as the boric acid of fusing assistant, according to formula M
x-asiO
5: the stoichiometric ratio in aRe weighs up, and after being ground, puts into corundum crucible, in High Temperature Furnaces Heating Apparatus 1200-1400 ℃ temperature range, under reducing atmosphere, through the calcination of above 3-6 hour once or once, obtains.
4. the preparation method of used for high-color developing energy-saving lamp rare earth silicate orange-red light flourescent material according to claim 3, is characterized in that: described reducing atmosphere is nitrogen hydrogen mixeding gas density of hydrogen 1-12%.
5. the preparation method of used for high-color developing energy-saving lamp rare earth silicate orange-red light flourescent material according to claim 4, is characterized in that: the fineness of described fluorescent material is less than 10um.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103980889A (en) * | 2014-04-30 | 2014-08-13 | 广东工业大学 | Silicate-based multi-color long-afterglow luminescent materials and preparation method thereof |
CN115537056A (en) * | 2022-08-18 | 2022-12-30 | 江苏博云塑业股份有限公司 | Rare earth silicate, radiation refrigeration composition, radiation refrigeration coating and preparation method |
Citations (2)
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US5839718A (en) * | 1997-07-22 | 1998-11-24 | Usr Optonix Inc. | Long persistent phosphorescence phosphor |
CN1745159A (en) * | 2003-03-28 | 2006-03-08 | 韩国化学研究所 | Strontium silicate-based phosphor, fabrication method thereof, and led using the phosphor |
-
2013
- 2013-11-04 CN CN201310541060.XA patent/CN103571462A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US5839718A (en) * | 1997-07-22 | 1998-11-24 | Usr Optonix Inc. | Long persistent phosphorescence phosphor |
CN1745159A (en) * | 2003-03-28 | 2006-03-08 | 韩国化学研究所 | Strontium silicate-based phosphor, fabrication method thereof, and led using the phosphor |
Non-Patent Citations (3)
Title |
---|
张梅等: "Sr3SiO5 :Eu2+, RE3+(RE=Sm, Dy, Ho, Er)的表征及其在LED上的应用", 《中国稀土学报》, 30 April 2009 (2009-04-30) * |
徐叙瑢等: "《发光学与发光材料》", 31 October 2004, article "发光在照明和其他光源中的应用" * |
洪广言: "《稀土发光材料基础与应用》", 30 January 2011, article "稀土发光材料的制备化学" * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103980889A (en) * | 2014-04-30 | 2014-08-13 | 广东工业大学 | Silicate-based multi-color long-afterglow luminescent materials and preparation method thereof |
CN103980889B (en) * | 2014-04-30 | 2016-06-22 | 广东工业大学 | A kind of silicate-base polychrome long after glow luminous material and preparation method thereof |
CN115537056A (en) * | 2022-08-18 | 2022-12-30 | 江苏博云塑业股份有限公司 | Rare earth silicate, radiation refrigeration composition, radiation refrigeration coating and preparation method |
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Application publication date: 20140212 |