CN104357043A - Fluorescent material as well as preparation method and application thereof - Google Patents
Fluorescent material as well as preparation method and application thereof Download PDFInfo
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- CN104357043A CN104357043A CN201410677729.2A CN201410677729A CN104357043A CN 104357043 A CN104357043 A CN 104357043A CN 201410677729 A CN201410677729 A CN 201410677729A CN 104357043 A CN104357043 A CN 104357043A
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- fluorescent material
- magnesium
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- alcohol
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Abstract
The invention relates to the technical field of a luminescent material, and in particular relates to a fluorescent material as well as a preparation method and application thereof. According to the fluorescent material, a silicon dioxide thin film is cladded on the surface of fluorescent powder which is taken as a matrix core, and nano magnesium oxide microcrystal is deposited on the surface of the silicon dioxide thin film, wherein the weight ratio of the silicon dioxide to the fluorescent powder is (1-8) to 100, and the weight ratio of the magnesium oxide microcrystal to the fluorescent powder is (6-15) to 100; and the silicon dioxide thin film is 15-120nm thick. The fluorescent material disclosed by the invention which is deposited with oxide on the surface is prepared by cladding the SiO2 thin film on the surface of the fluorescent powder and depositing the MgO microcrystal on the thin film, so that thermal stability and degradation resistance of the fluorescent powder in a screening burning or tube burning process are enhanced, the service life of the fluorescent powder is prolonged and luminous efficiency is improved.
Description
Technical field
The present invention relates to luminescent material technical field, be specifically related to a kind of fluorescent material and its preparation method and application.
Background technology
In many illuminations and display equipment, fluorescent material is vital luminescent material, is widely used in the fields such as illumination, display, detection, mark.Fluorescent material of a great variety, but in use still there is certain obstinate problem in fluorescent material, the problems such as such as, thermostability is low, easy deterioration.
At the coated one deck mineral membrane of phosphor surface, oxygen can be avoided the direct effect of fluorescent material, to reach the object alleviating deterioration.MgO has excellent characteristic, such as high secondary electron yield, resistance to ion bombardment, surface resistivity advantages of higher and be widely used in display field.Electron rays can be converted into visible ray by MgO, MgO thus can be utilized to carry out coated to fluorescent material, improve the luminous efficiency of fluorescent material, and improves the resist degradation performance of fluorescent material.
Summary of the invention
The present inventor studies rear discovery, utilizes traditional liquid phase method not easily to form fine and close MgO film at phosphor surface, makes effectively to play the effect of the aspects such as the chemoresistance that improves fluorescent material and luminous efficiency.
Namely, the technical problem that the present invention solves is: although the coated fluorescent material performance of existing magnesium oxide makes moderate progress, but because traditional liquid phase method not easily forms fine and close MgO film at phosphor surface, therefore its performance such as chemoresistance and luminous efficiency thereof need to improve.
For solving the problems of the technologies described above, the present inventor through untiringly research after find: except silicon dioxide layer can phosphor surface carry out densification coated except, other traditional coating materials, as magnesium oxide, aluminum oxide, the mixture of both mixtures or itself and silicon-dioxide is difficult to form fine and close protective layer at phosphor surface, thus the raising of the performance such as resistant to hydrolysis performance and luminous efficiency of fluorescent material is not easily realized, therefore the invention provides a kind of preparation method at fluorescent material outside deposition oxide compound: by phosphor surface covering silicon dioxide film, deposition of magnesium crystallite thereon again.The method is simple, workable.After fluorescent material is wrapped by, not only chemoresistance is improved, and luminous efficiency also increases to some extent simultaneously.
Specifically, for the deficiencies in the prior art, the invention provides following technical scheme:
The invention provides a kind of fluorescent material, it is characterized by, take fluorescent material as matrix core, to be coated with silicon oxide film, to have nano magnesia crystallite at silica membrane surface deposition at phosphor surface; Wherein, the weight ratio of described silicon-dioxide and fluorescent material is (1-8): 100, and the weight ratio of described magnesium oxide crystallite and fluorescent material is (2-15): 100; And the thickness of described silica membrane is 15-120nm.
Preferably, in above-mentioned fluorescent material, the particle diameter of the described fluorescent material as matrix core is 1-10 μm.
Preferably, in above-mentioned fluorescent material, described magnesium oxide crystallite is of a size of 20-200nm, and the pattern of described magnesium oxide crystallite is cube or class cube.
Preferably, in above-mentioned fluorescent material, the described fluorescent material as matrix core is selected from silicate series, nitride series, molybdate is serial, series of phosphate, molybdate series, aluminate serial, borate serial or sulfide is serial.
Preferably, in above-mentioned fluorescent material, the described fluorescent material as matrix core is selected from silicate series, series of phosphate or sulfide series.
Preferably, in above-mentioned fluorescent material, the maximum emission wavelength scope of the described fluorescent material as matrix core is 620-770nm, 490-570nm or 455-490nm.
Preferably, in above-mentioned fluorescent material, the quantum yield of described fluorescent material improves 10-13% than the quantum yield as the fluorescent material of matrix core.
The present invention also provides the preparation method of above-mentioned fluorescent material, comprises the steps:
(1) fluorescent material, tetraethoxy are mixed with mixed solution A, the fluorescent material of the obtained film that is coated with silicon oxide; Wherein, described mixed solution A comprises water, alcohol and strong aqua;
(2) being scattered in mixing solutions B by step (1) gained fluorescent material, is react under the alkaline condition of 9-13 in pH, in step (1) gained phosphor surface deposition magnesium hydroxide; Wherein, described mixing solutions B comprises magnesium salts, dispersion agent, water and alcohol;
(3) after step (2) gained fluorescent material being calcined at 550-750 DEG C, obtained fluorescent material.
Preferably, in above-mentioned preparation method, alcohol described in mixed solution A is selected from ethanol, Virahol or propyl carbinol; Described in mixing solutions B, alcohol is selected from ethanol or Virahol.
Preferably, in above-mentioned preparation method, alcohol described in mixed solution A is ethanol, and alcohol described in mixing solutions B is ethanol.
Preferably, in above-mentioned preparation method, the mixing step of step (1) refers to tetraethoxy (TEOS) dropwise to add in the mixing solutions of fluorescent material and mixed solution A.
Preferably, in above-mentioned preparation method, the volume ratio of alcohol and water described in described mixed solution A is (1.5-2.5): 1.
Preferably, in above-mentioned preparation method, in described tetraethoxy and mixed solution A, the weight ratio of water is (0.32-2.6): 100.
Preferably, in above-mentioned preparation method, in described tetraethoxy and mixed solution A, the weight ratio of ammoniacal liquor is (0.08-0.35): 1.
Preferably, in above-mentioned preparation method, in described mixing solutions B, magnesium salts is selected from the magnesium chloride of crystal water or nodeless mesh water, magnesium acetate, Magnesium Stearate, magnesium citrate, alkoxyl magnesium or magnesium acetylacetonate.
Preferably, in above-mentioned preparation method, in described mixing solutions B, dispersion agent is selected from polyoxyethylene glycol, ethylene glycol, propylene glycol, alkylphenol polyoxyethylene or Triton X-100, and wherein, the quality of dispersion agent is the 5-60% of magnesium salts quality.
Preferably, in above-mentioned preparation method, described in described mixing solutions B, the volume ratio of alcohol and water is (0.5-2): 1.
Preferably, in above-mentioned preparation method, before step (1), also comprise the pre-treatment of fluorescent material, described pre-treatment comprises the steps: phosphor particles to be scattered in ethanol, Virahol or propyl carbinol.
The invention provides a kind of fluorescent material, prepared by above-mentioned preparation method.
The present invention also provides above-mentioned fluorescent material in the application of plasma display apparatus, plasma ultraviolet source, luminescent lamp, low pressure mercury lamp and white light LED part.
The effect that the present invention produces is: first the present invention utilizes
method (namely utilize alcohol to make solvent, make tetraethoxy hydrolysis under ammonia-catalyzed, tridimensional network that polycondensation, polymerization obtain silicon-dioxide) is at the SiO of the coated densification of phosphor surface
2film, the method is simple, workable.SiO is carried out to fluorescent material
2film coated, can repair the defect of phosphor surface, improves the planeness of phosphor surface, reduces the absorption to outgoing or incident light and scattering; In addition, by fine and close SiO
2coated, effectively can isolate the oxygen of outside invading, thus improve the resist degradation performance of fluorescent material.Secondly, at SiO
2film utilize heterogeneous precipitation method continue depositing nano MgO microcrystal grain.Nano-MgO microporous surface is long-pending large, and surfactivity is high, has stronger water-retaining capacity, but can not very fast and water react, and this ensure that MgO can not change Mg (OH) easily in preparation process
2or MgCO
3, thus fluorescent material hydrolysis problem in use can be solved, improve the chemoresistance of fluorescent material further.In addition, MgO can change electron rays into visible ray, improves the luminous efficiency of fluorescent material.
Embodiment
The invention provides a kind of fluorescent material and its preparation method and application, preparation method comprises the steps: to take fluorescent material as matrix core, utilizes
method is at the SiO of the coated densification of fluorescent material outside surface
2film, obtains fluorescent material@SiO
2, that is, take fluorescent material as matrix core ,@is meant to " coated ", SiO
2for shell; Then utilize heterogeneous precipitation method at SiO
2film continues depositing nano MgO crystallite fluorescent material@MgO.
In a kind of preferred embodiment, the preparation method of fluorescent material of the present invention comprises the steps:
(1) phosphor particles EtOH Sonicate process, then by this Solution Dispersion in the mixing solutions of water, ethanol, strong aqua, after fully mixing, in solution, dropwise add TEOS (tetraethoxy), stirred at ambient temperature, filters and obtains fluorescent material@SiO
2;
(2) then it is dispersed in again in the mixing solutions containing magnesium salts, dispersion agent, deionized water and ethanol, under vigorous stirring, add the mixing solutions of the second alcohol and water containing sodium hydroxide, adjust ph is 9-13 stopped reaction, after ageing for some time, filter with deionized water and absolute ethanol washing, then vacuum-drying, obtains fluorescent material SiO
2@Mg (OH)
2;
(3) by fluorescent material@SiO
2@Mg (OH)
2calcine at a certain temperature, obtain fluorescent material@SiO
2@MgO.
The present invention can select the fluorescent material of emission wavelength within the scope of 440-760nm, by phosphor surface coated Si O
2film, then deposit MgO crystallite thereon, the work-ing life of improving the thermostability of fluorescent material in roasting screen or roasted tube process, resist degradation, increase fluorescent material can be realized, and improve the object of luminous efficiency.
The preparation method and application of fluorescent material of the present invention are further illustrated below by specific embodiment.
In the following embodiments, the information of each reagent used is as shown in table 1.
Agents useful for same information table in table 1 embodiment
Embodiment one
By 10g red fluorescence powder Y
2o
2s:Eu
3+with ethanol (50mL) supersound process 30min, then the mixing solutions of this fluorescent material and ethanol is dispersed in deionized water (100mL), ethanol (150mL), strong aqua (28%, in mixing solutions 8mL), 0.32g TEOS (tetraethoxy) is dropwise added in solution, stirred at ambient temperature 6h, filters and obtains Y
2o
2s:Eu
3+@SiO
2;
Then it is dispersed in again containing magnesium citrate nonahydrate (1.03g), OP-10 (alkylphenol polyoxyethylene, in the mixing solutions of 1.86g), deionized water (100mL) and ethanol (100mL), under vigorous stirring, add the mixing solutions of ethanol (0.5mL) containing sodium hydroxide (0.04g) and water (1mL), adjust ph is 9, stopped reaction, after ageing 12h, successively filter with deionized water and absolute ethanol washing respectively, then vacuum-drying, obtains Y
2o
2s:Eu
3+@SiO
2@Mg (OH)
2;
Finally by Y
2o
2s:Eu
3+@SiO
2@Mg (OH)
2in nitrogen atmosphere, calcining at 750 DEG C, obtain Y
2o
2s:Eu
3+@SiO
2@MgO.
Diameter characterization: the present invention adopts laser particle size measurement instrument (Mastersizer 3000), wet method sample introduction is benchmark with volume, records non-coated Si O
2the median size (D of red fluorescence powder
50) be 1-3 μm, adopt JEM-2010 transmission electron microscope can obtain coated rear SiO
2film thickness is about 15nm, and the particle diameter recording magnesium oxide microcrystal grain with same method is 20-80nm.
Spectroscopic analysis: the present invention adopts fluorescence spectrophotometer (Horiba FluoroMax-4), is excitation wavelength, records non-coated Si O with 325nm
2the maximum emission wavelength of red fluorescence powder be 625nm, Y
2o
2s:Eu
3+@SiO
2the maximum emission wavelength of@MgO is 625nm.
Luminous efficiency: measure non-coated Si O
2red fluorescence powder and Y
2o
2s:Eu
3+@SiO
2the quantum yield of@MgO, characterizes its luminous efficiency.Concrete grammar is as follows: Horiba FluoroMax-4 prepares integrating sphere, can provide quantum yield automatically by FluoroMax-4 system software.Result shows, not coated Y
2o
2s:Eu
3+quantum yield is 0.37, the Y after coated
2o
2s:Eu
3+@SiO
2the quantum yield of@MgO improves 10% than the quantum yield of not coated red fluorescence powder.After placing 30 days, not coated light-emitting phosphor intensity reduces by 20%, and the light-emitting phosphor intensity after coated is substantially constant.
Embodiment two
By 10g green emitting phosphor Ca
8mg (SiO
4)
4cl
2: Eu
2+with ethanol (50mL) supersound process 30min, then the mixing solutions of this fluorescent material and ethanol is dispersed in deionized water (100mL), ethanol (200mL), strong aqua (28%, in mixing solutions 60mL), 1.30g TEOS is dropwise added in solution, stirred at ambient temperature 12h, filters and obtains Ca
8mg (SiO
4)
4cl
2: Eu
2+@SiO
2;
Then it is dispersed in again in the mixing solutions containing four acetate hydrate magnesium (4.3g), ethylene glycol (1.3g), deionized water (100mL) and ethanol (100mL), under vigorous stirring, add the mixing solutions of ethanol (40mL) containing sodium hydroxide (1.6g) and deionized water (40mL), adjust ph is 11, stopped reaction, after ageing 16h, successively filter with deionized water and absolute ethanol washing respectively, then vacuum-drying, obtains Ca
8mg (SiO
4)
4cl
2: Eu
2+@SiO
2@Mg (OH)
2;
Finally by Ca
8mg (SiO
4)
4cl
2: Eu
2+@SiO
2@Mg (OH)
2in nitrogen atmosphere, calcining at 600 DEG C, obtain Ca
8mg (SiO
4)
4cl
2: Eu
2+@SiO
2@MgO.
Diameter characterization: the present invention adopts laser particle size measurement instrument (Mastersizer 3000), wet method sample introduction is benchmark with volume, records non-coated Si O
2the D of green emitting phosphor
50for 3-6 μm, adopt JEM-2010 transmission electron microscope can obtain coated rear SiO
2film thickness is 60nm, and the particle diameter recording magnesium oxide microcrystal grain with same method is 80-150nm.
Spectroscopic analysis: the present invention adopts fluorescence spectrophotometer (Horiba FluoroMax-4), is excitation wavelength, records non-coated Si O with 460nm
2the maximum emission wavelength of green emitting phosphor be 510nm, Ca
8mg (SiO
4)
4cl
2: Eu
2+@SiO
2the maximum emission wavelength of@MgO is 510nm.
Luminous efficiency: measure non-coated Si O
2green emitting phosphor and Ca
8mg (SiO
4)
4cl
2: Eu
2+@SiO
2the quantum yield of@MgO, characterizes its luminous efficiency.Concrete grammar is as follows: Horiba FluoroMax-4 prepares integrating sphere, can provide quantum yield automatically by FluoroMax-4 system software.Result shows, not coated Ca
8mg (SiO
4)
4cl
2: Eu
2+quantum yield be 0.56, the Ca after coated
8mg (SiO
4)
4cl
2: Eu
2+@SiO
2the quantum yield of@MgO improves 13% than the quantum yield of not coated green emitting phosphor.After placing 30 days, not coated light-emitting phosphor intensity reduces by 15%, and the light-emitting phosphor intensity after coated is substantially constant.
Embodiment three
By 10g blue colour fluorescent powder Sr
5(PO
4)
3cl:Eu
2+with ethanol (50mL) supersound process 30min, then the mixing solutions of this fluorescent material and ethanol is dispersed in deionized water (100mL), ethanol (250mL), strong aqua (28%, in mixing solutions 32mL), 2.60g TEOS is dropwise added in solution, stirred at ambient temperature 8h, filters and obtains Sr
5(PO
4)
3cl:Eu
2+@SiO
2;
Then it is dispersed in again in the mixing solutions containing Magnesium dichloride hexahydrate (7.62g), poly(oxyethylene glycol) 400 (0.38g), deionized water (100mL) and ethanol (100mL), under vigorous stirring, add the mixing solutions of ethanol (150mL) containing sodium hydroxide (3g) and deionized water (75mL), adjust ph is 13, stopped reaction, after ageing 16h, filter with deionized water and absolute ethanol washing, then vacuum-drying, obtains Sr
5(PO
4)
3cl:Eu
2+@SiO
2@Mg (OH)
2;
Finally by Sr
5(PO
4)
3cl:Eu
2+@SiO
2@Mg (OH)
2in nitrogen atmosphere, calcining at 550 DEG C, obtain Sr
5(PO
4)
3cl:Eu
2+@SiO
2@MgO.
Diameter characterization: the present invention adopts laser particle size measurement instrument (Mastersizer 3000), wet method sample introduction is benchmark with volume, records non-coated Si O
2the D of blue colour fluorescent powder
50for 6-10 μm, employing and JEM-2010 transmission electron microscope can obtain coated rear SiO
2film thickness is 120nm, and the particle diameter recording magnesium oxide microcrystal grain with same method is 100-200nm.
Spectroscopic analysis: the present invention adopts fluorescence spectrophotometer (Horiba FluoroMax-4), is excitation wavelength, records non-coated Si O with 360nm
2the maximum emission wavelength of blue colour fluorescent powder be 465nm, Sr
5(PO
4)
3cl:Eu
2+@SiO
2the maximum emission wavelength of@MgO is 465nm.
Luminous efficiency: measure non-coated Si O
2blue colour fluorescent powder and Sr
5(PO
4)
3cl:Eu
2+@SiO
2the quantum yield of@MgO, characterizes its luminous efficiency.Concrete grammar is as follows: Horiba FluoroMax-4 prepares integrating sphere, can provide quantum yield automatically by FluoroMax-4 system software.Result shows, not coated Sr
5(PO
4)
3cl:Eu
2+quantum yield be 0.83, the Sr after coated
5(PO
4)
3cl:Eu
2+@SiO
2the quantum yield of@MgO improves 11% than the quantum yield of not coated blue colour fluorescent powder.After placing 30 days, not coated light-emitting phosphor intensity reduces by 17%, and the light-emitting phosphor intensity after coated is substantially constant.
By obtain in above-described embodiment coated after fluorescent material and each 3g of not coated fluorescent material add respectively in 20g water, stir, leave standstill 2h, found that not coated phosphor surface turns white, occur hydrolysis phenomena.Adopt coated after the essentially no change of fluorescent material, illustrate coated after fluorescent material resistant to hydrolysis ability strengthen.
In sum, the fluorescent material prepared by the present invention is compared with not coated fluorescent material, and luminous efficiency is significantly increased, and work-ing life strengthens, and resistant to hydrolysis performance enhancement, superior performance, has broad application prospects.
Claims (20)
1. a fluorescent material, is characterized by, and take fluorescent material as matrix core, to be coated with silicon oxide film, to have nano magnesia crystallite at silica membrane surface deposition at phosphor surface; Wherein, the weight ratio of described silicon-dioxide and fluorescent material is (1-8): 100, and the weight ratio of described magnesium oxide crystallite and fluorescent material is (2-15): 100; And the thickness of described silica membrane is 15-120nm.
2. fluorescent material according to claim 1, wherein, the particle diameter of the described fluorescent material as matrix core is 1-10 μm.
3. fluorescent material according to claim 1 and 2, wherein, described magnesium oxide crystallite is of a size of 20-200nm.
4. the fluorescent material according to any one of claim 1-3, wherein, the described fluorescent material as matrix core is selected from silicate series, nitride series, molybdate is serial, series of phosphate, molybdate series, aluminate serial, borate serial or sulfide is serial.
5. fluorescent material according to claim 4, wherein, the described fluorescent material as matrix core is selected from silicate series, series of phosphate or sulfide series.
6. the fluorescent material according to any one of claim 1-5, wherein, the maximum emission wavelength scope of the described fluorescent material as matrix core is 620-770nm or 455-570nm.
7. the fluorescent material according to any one of claim 1-6, wherein, the quantum yield of described fluorescent material improves 10-13% than the quantum yield as the fluorescent material of matrix core.
8. the preparation method of the fluorescent material described in any one of claim 1-7, comprises the steps:
(1) fluorescent material, tetraethoxy are mixed with mixed solution A, the fluorescent material of the obtained film that is coated with silicon oxide; Wherein, described mixed solution A comprises water, alcohol and strong aqua;
(2) being scattered in mixing solutions B by step (1) gained fluorescent material, is react under the alkaline condition of 9-13 in pH, in step (1) gained phosphor surface deposition magnesium hydroxide; Wherein, described mixing solutions B comprises magnesium salts, dispersion agent, water and alcohol;
(3) after step (2) gained fluorescent material being calcined at 550-750 DEG C, obtained fluorescent material.
9. preparation method according to claim 8, wherein, alcohol described in mixed solution A is selected from ethanol, Virahol or propyl carbinol; Described in mixing solutions B, alcohol is selected from ethanol or Virahol.
10. preparation method according to claim 8 or claim 9, wherein, alcohol described in mixed solution A is ethanol, and alcohol described in mixing solutions B is ethanol.
11. preparation methods according to claim 8, wherein, the mixing step of step (1) refers to dropwise be added by tetraethoxy in the mixing solutions of fluorescent material and mixed solution A.
12. preparation methods according to Claim 8 described in-11 any one, wherein, the volume ratio of alcohol and water described in described mixed solution A is (1.5-2.5): 1.
13. preparation methods according to Claim 8 described in-12 any one, wherein, in described tetraethoxy and mixed solution A, the weight ratio of water is (0.32-2.6): 100.
14. preparation methods according to Claim 8 described in-13 any one, wherein, in described tetraethoxy and mixed solution A, the weight ratio of ammoniacal liquor is (0.08-0.35): 1.
15. preparation methods according to Claim 8 described in-14 any one, wherein, in described mixing solutions B, magnesium salts is selected from the magnesium chloride of crystal water or nodeless mesh water, magnesium acetate, Magnesium Stearate, magnesium citrate, alkoxyl magnesium or magnesium acetylacetonate.
16. preparation methods according to Claim 8 described in-15 any one, wherein, in described mixing solutions B, dispersion agent is selected from polyoxyethylene glycol, ethylene glycol, propylene glycol, alkylphenol polyoxyethylene or Triton X-100, and wherein, the quality of dispersion agent is the 5-60% of magnesium salts quality.
17. preparation methods according to Claim 8 described in-16 any one, wherein, described in described mixing solutions B, the volume ratio of alcohol and water is (0.5-2): 1.
18. preparation methods according to Claim 8 described in-11 any one, before step (1), also comprise the pre-treatment of fluorescent material, described pre-treatment comprises the steps: phosphor particles to be scattered in ethanol, Virahol or propyl carbinol.
19. 1 kinds of fluorescent materials, are prepared by the preparation method described in any one of claim 8-18.
Described in 20. claim 1-7 or any one of claim 19, fluorescent material is in the application of plasma display apparatus, plasma ultraviolet source, luminescent lamp, low pressure mercury lamp and white light LED part.
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| CN108341607A (en) * | 2018-03-13 | 2018-07-31 | 武汉理工大学 | A kind of silica modified magnesia and its preparation method and application |
| WO2019000671A1 (en) * | 2017-06-28 | 2019-01-03 | 深圳市光峰光电技术有限公司 | Composite ceramic and preparation method therefor |
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| WO2019000671A1 (en) * | 2017-06-28 | 2019-01-03 | 深圳市光峰光电技术有限公司 | Composite ceramic and preparation method therefor |
| US11097984B2 (en) | 2017-06-28 | 2021-08-24 | Appotronics Corporation Limited | Composite ceramic and preparation method therefor |
| CN108341607A (en) * | 2018-03-13 | 2018-07-31 | 武汉理工大学 | A kind of silica modified magnesia and its preparation method and application |
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