CN100572497C - The preparation method of high brilliancy environmental protection type alkaline earth ion solid solution titanate fluorescent powder - Google Patents
The preparation method of high brilliancy environmental protection type alkaline earth ion solid solution titanate fluorescent powder Download PDFInfo
- Publication number
- CN100572497C CN100572497C CNB200610053079XA CN200610053079A CN100572497C CN 100572497 C CN100572497 C CN 100572497C CN B200610053079X A CNB200610053079X A CN B200610053079XA CN 200610053079 A CN200610053079 A CN 200610053079A CN 100572497 C CN100572497 C CN 100572497C
- Authority
- CN
- China
- Prior art keywords
- alkaline earth
- compound
- preparation
- earth ion
- ball milling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000843 powder Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000006104 solid solution Substances 0.000 title claims abstract description 15
- 230000007613 environmental effect Effects 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 118
- -1 ion titanate Chemical class 0.000 claims abstract description 24
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 22
- 239000012298 atmosphere Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000010304 firing Methods 0.000 claims abstract description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 54
- 238000000498 ball milling Methods 0.000 claims description 52
- 150000002500 ions Chemical class 0.000 claims description 37
- 239000002994 raw material Substances 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 17
- 229910002651 NO3 Inorganic materials 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 14
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 150000002910 rare earth metals Chemical class 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 239000010431 corundum Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 206010013786 Dry skin Diseases 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 239000004530 micro-emulsion Substances 0.000 claims description 4
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 claims description 4
- 238000006068 polycondensation reaction Methods 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims description 2
- 230000002349 favourable effect Effects 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 240000003936 Plumbago auriculata Species 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 11
- 238000010894 electron beam technology Methods 0.000 abstract description 7
- 230000005284 excitation Effects 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- 238000011017 operating method Methods 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 30
- 238000000227 grinding Methods 0.000 description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 20
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 16
- 239000000126 substance Substances 0.000 description 16
- 239000010936 titanium Substances 0.000 description 15
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 15
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 14
- 238000005303 weighing Methods 0.000 description 11
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 10
- 229910000018 strontium carbonate Inorganic materials 0.000 description 10
- 239000004408 titanium dioxide Substances 0.000 description 10
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- 241000209456 Plumbago Species 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005424 photoluminescence Methods 0.000 description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 229910052691 Erbium Inorganic materials 0.000 description 3
- 229910052693 Europium Inorganic materials 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 229910052771 Terbium Inorganic materials 0.000 description 3
- 229910052775 Thulium Inorganic materials 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 3
- 231100000956 nontoxicity Toxicity 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 3
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 3
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 229910001864 baryta Inorganic materials 0.000 description 2
- 238000005136 cathodoluminescence Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 231100000957 no side effect Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- WCWKKSOQLQEJTE-UHFFFAOYSA-N praseodymium(3+) Chemical compound [Pr+3] WCWKKSOQLQEJTE-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical compound CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Landscapes
- Luminescent Compositions (AREA)
Abstract
The invention discloses compositing formula of the rare-earth ion activated alkaline earth ion solid solution titanate fluorescent powder of a kind of high brilliancy environmental protection type and preparation method thereof.Feature of the present invention is on the rare-earth ion activated alkaline earth titanate fluorescent powder matrix basis that single alkaline earth element constitutes, replace and high-temperature atmosphere such as burns till at means by the element between alkaline earth ion, prepare the alkaline earth ion solid solution titanate fluorescent powder that excites and have high luminosity and material use properties during burst of ultraviolel in denoted low voltage electron beam.Firing atmosphere can be selected air, CO, N
2Or H
2In pure gas or its mixed gas.This method is compared with traditional single alkaline earth ion titanate fluorescent powder, has the advantages that operating procedure is simple, cost is low, fluorescent material brightness is high.Advantageous characteristic such as that this fluorescent material has is nontoxic, stability of material height can be widely used in field of information display such as electron-beam excitation display screen.
Description
Technical field
The present invention relates to a kind of high brilliancy environmental protection type alkaline earth ion solid solution titanate fluorescent powder and preparation method thereof, specifically be meant a kind of compositing formula that burns till the rare-earth ion activated alkaline earth ion solid solution titanate fluorescent powder of preparation high brilliancy environmental protection type by element substituting effect between alkaline earth ion and high-temperature atmosphere and preparation method thereof, belong to materials science field.
Background technology
Along with developing rapidly of modern science and technology, luminescent material develops into by multiple excitaton source stimulated luminescences such as electricity, sound, heat, chemistry, biology, mechanical energy and energetic rays from general photoluminescence, demonstration and an illuminating material, and be widely used in ultra-thin television, liquid crystal and plasma display, the crucial display material of high-tech products such as mini monitor and sophisticated sensor and probe.
In the recent period, Field Emission Display (FED) has obtained flourish as a kind of emerging flat panel display, and is expected to replace conventional cathode ray tube (CRT) technique of display, and FED requires to work under the condition of low voltage and high current density with fluorescent material, traditional C RT fluorescent material is as red Y commonly used
2O
3: Eu fluorescent material just can not be used in FED and show occasion.At present, (10V～100V) red fluorescence powder of electron-beam excitation mainly is Zn to be used for low pressure
1-xCd
xS (0≤x≤1) system fluorescent material, this fluorescent material has been widely used in vacuum fluorescent display device occasions such as (VFD).Yet, sulfide Zn
1-xCd
xIn use there are some tangible problems in S fluorescent material, decomposes easily as long-time electron beam irradiation postcure matter fluorescent powder, and decomposes S or the SO that produces
2Reduced electron emissivity as the electron source oxide cathode; In addition, a large amount of ruddiness colourity conditioning agent component Cd ion pair human body harmfuls that adopt in this sulphide fluorescent material, European Union considers from the environmental protection equal angles, stipulates to begin to forbid such Zn in July, 2006
1-xCd
xThe S red fluorescence powder, this has caused traditional Z n1
-xCd
xThe Application Areas of S red fluorescence powder is subjected to very big restriction, presses for the searching and the nontoxicity of development of new, the desirable red FED fluorescent material of efficient stable at present.
People such as Vecht in 1994 have at first found the CaTiO of perovskite structure
3: pr
3+, and think that it is a kind of novel red fluorescent material with potential demonstration purposes.1996, people such as Toki found Al (OH)
3Or Ga
2O
3The component codoped can make SrTiO
3: Pr
3+About two orders of magnitude of photoluminescence and cathodoluminescence intensity enhancing can be used as the red fluorescence powder material of Field Emission Display (FED) and the luminous demonstration of vacuum electronic (VFD) etc.Therefore, the research and development of titanate substrate fluorescent powder has caused the concern of industrial community.With Zn
1-xCd
xThe S sulphide fluorescent material is compared, and the materials chemistry character of titanate substrate fluorescent powder is highly stable, and when adopting rare earth ion as the luminescence center ion, the glow peak of fluorescent material is single, and purity of color is better, as CaTiO
3: Pr
3+Photoluminescence and the chromaticity coordinates of negative ray ruddiness be x=0.680, y=0.311, very approaching with the desirable redness of U.S. NTSC system regulation.Consider that from stability of material and glow color such rare-earth ion activated titanate fluorescent powder is expected to substitute Zn
1-xCd
xThe sulfide red fluorescent material of S becomes the nontoxicity of a new generation, the desirable red FED phosphor material powder of high stable.
But still there is luminosity fundamental issue on the low side in this class material, has limited its application.So far, the patent application of relevant this class fluorescent material is seldom recorded in 2004 and 2005 as big island English and have been applied for patent 2004-097738 and 200510069719.1 in Japan and China respectively.In addition, at CaTiO
3The relation research of the material structure of fluorescent material and luminescent properties, more non-patent literature report is arranged, as non-patent literature 1 (Vecht etc., " New electron excited light emittingmaterials ", J.Vac.Sci.Tehcnol.B, 12 (2) (1994) p.781), non-patent literature 2 (Diallo etc., " Improvement of the optical performances of pr
3+In CaTiO
3", J.Alloys.Compd., 323-324 (2001) are p.218); Or non-patent literature 3 (Kang etc., " Theinfluence of Li addition on Cathodoluminescence of CaTiO
3: Pr
3+", Eurodisplay (2002) is p.777).
Summarize present existing patent documentation and non-patent literature report and find that the pyroreaction firing process under traditional air atmosphere is all adopted in all literature research work, and research work mainly is the Ti to single alkaline earth ion titanate matrix
4+Ion improves the luminosity of red titanate fluorescent material with different sorts divalence or trivalent assisting ion doped and substituted, and analyzes and researches at material structure and luminescent properties.These dopant ion valence state and Ti
4+The ionic valence condition difference, therefore mixing has caused extra charge defects, thereby has influenced the luminescent properties of fluorescent material.Although part document and patent report under photoluminescence and the electron-beam excitation light-emitting phosphor brightness be significantly improved, but back phosphor material powder sclerosis, shortcomings such as material expected service life reduction take place to change mutually, burn till in the matrix that easily causes a large amount of dopant ions that for this reason mix.
On the whole, the luminosity of this class material is still lower at present, needs to continue to improve and improve.Consider from material structure, at present still do not utilize the element substituting effect between alkaline earth ion in fluorescent material matrix, to introduce lattice distortion, change rare-earth luminescent center ion chemical environment on every side, and regulate and control the matrix structure defective of fluorescent material in conjunction with some special preparation process conditions, thereby obtain the research report of the fluorescent material of high brightness, also do not have relevant patent application.
Summary of the invention
The present invention be at present broad research to single alkaline earth ion titanate matrix Ti
4+Ion improves the luminosity of red titanate fluorescent material with different sorts divalence or trivalent assisting ion doped and substituted, carrying out material prescription improves outside the technological line, for improving the material service performances such as luminosity of phosphor material powder, proposition utilizes the element substituting effect between alkaline earth ion to introduce lattice distortion in fluorescent material matrix, change rare-earth luminescent center ion chemical environment on every side, and regulate and control the matrix structure defective of fluorescent material, thereby obtain environmental protection type alkaline earth ion solid solution titanate fluorescent powder of high brightness and preparation method thereof in conjunction with some special preparation process conditions.The invention provides a kind of when not introducing the ion doping of charge defects, only just can obtain the new preparation process of high brightness red alkaline earth titanate fluorescent powder by the element substituting effect between alkaline earth ion and corresponding firing atmosphere kind and flow, the luminous intensity that its burst of ultraviolel and denoted low voltage electron beam excite can improve an order of magnitude.
A kind of high brilliancy environmental protection type alkaline earth ion solid solution titanate fluorescent powder, its prescription composition formula is (Ca
1-x-ySr
xBa
y) TiO
3: zRe, δ M, wherein 0≤x＜1.0,0≤y＜1.0 and 0＜x+y≤1.0,0＜z≤0.15,0≤δ≤0.4; Re is Doped Rare Earth luminescence center ion (or claiming rare-earth ion activated dose), is among praseodymium Pr, cerium Ce, europium Eu, terbium Tb, erbium Er or the thulium Tm one or both; M is the supplementary doping element, is among boron, aluminium Al, gallium Ga, indium In, lithium Li, sodium Na or the potassium K one or more.
A kind of preparation method of high brilliancy environmental protection type alkaline earth ion solid solution titanate fluorescent powder may further comprise the steps:
1) burns till with the preparation of solid phase batch mixing method or wet-chemical reaction method and use compound.
2) will burn till plumbago crucible or the corundum matter tube furnace of putting into high-temperature electric resistance furnace, favorable sealing property with compound, blowing air, CO, N
2Or H
2In a kind of gas or its mixed gas, begin to be warming up to 900～1400 ℃ from room temperature, carried out sufficient pyroreaction in 1～6 hour in the firing temperature insulation of setting, after insulation finishes with 10 ℃/min, keep the firing atmosphere furnace cooling to room temperature, obtain to burn till the fluorescence powder.
3) be 1: 0.5～2.5 adding dehydrated alcohols by the weight ratio of burning till fluorescence powder and dehydrated alcohol, at rotating speed is that ball milling mixes 4～24h in 50～250r/min planetary ball mill, the ball milling material was dried 6～24 hours in 50～150 ℃ of baking ovens, after oven dry material sieves promptly.
Described solid phase batch mixing method is: with alkaline earth carbonate, TiO
2, rare earth nitrate and supplementary doping element M compound be raw material, pressing atomic ratio is (Ca
1-x-ySr
xBa
y) TiO
3: zRe, δ M prepares the raw material compound, wherein 0≤x＜1.0,0≤y＜1.0 and 0＜x+y≤1.0,0＜z≤0.15,0≤δ≤0.4; Re is a Doped Rare Earth luminescence center ion, is one or both of praseodymium Pr, cerium Ce, europium Eu, terbium Tb, erbium Er or thulium Tm; M is the supplementary doping element, is one or more of boron, aluminium Al, gallium Ga, indium In, lithium Li, sodium Na or potassium K; Weight ratio by raw material compound and deionized water is 1: 0.5～1.5, adds deionized water, and ball milling mixes 2～12h in rotating speed 200r/min planetary ball mill, and the ball milling material was dried 10～48 hours in 50～150 ℃ of baking ovens, promptly got to burn till to use compound.
Described wet-chemical reaction method is: adopting compound, butyl (tetra) titanate and the rare earth nitrate of alkaline earth nitrate, supplementary doping element M is raw material, and is assistant chemical reagent with hexanaphthene, polyoxyethylene glycol Octyl Ether and methyl ethyl diketone; Pressing atomic ratio is (Ca
1-x-ySr
xBa
y) TiO
3: zRe, δ M takes by weighing each raw material, wherein 0≤x＜1.0,0≤y＜1.0 and 0＜x+y≤1.0,0＜z≤0.15,0≤δ≤0.4; Re is a Doped Rare Earth luminescence center ion, is one or both of praseodymium Pr, cerium Ce, europium Eu, terbium Tb, erbium Er or thulium Tm; M is the supplementary doping element, is one or more of boron, aluminium Al, gallium Ga, indium In, lithium Li, sodium Na or potassium K; The rare earth nitrate raw material is added deionized water, and adjusting solution middle-weight rare earths ionic concn is 0.5～2.0mol/L, and pH value of solution is 2～6; Get 50～150ml hexanaphthene, agitation condition adds 10～50ml surfactant polyethylene Octyl Ether down, add nitric acid diluent then by proportioning blended rare earth nitrate solution 2～10ml, alkaline earth nitrate solution and supplementary doping element compound, add again primary isoamyl alcohol to solution transparent till, continue to stir 10～60 minutes; The butyl (tetra) titanate raw material that adds again by proportional quantity is hydrolyzed and polycondensation, control its hydrolysis rate by the dissemination of water in the microemulsion, form the gel main body of homogeneous transparent at last, it 50～250 ℃ of dryings, is promptly got to burn till after the exsiccant xerogel grinds and use compound.
Described alkaline earth carbonate is CaCO
3, SrCO
3Or BaCO
3One or more.
Described alkaline earth nitrate is Ca (NO
3)
2, Sr (NO
3)
2Or Ba (NO
3)
2One or more.
The compound of described supplementary doping element M is oxide compound, oxyhydroxide or the carbonate cpds of supplementary doping element M.
The compound of described supplementary doping element M is B
2O
3, Al (OH)
3, Ga
2O
3, In
2O
3, Li
2CO
3, Na
2CO
3Or K
2CO
3In one or more.
Described rare earth nitrate is Pr (NO
3)
3, Ce (NO
3)
3, Eu (NO
3)
3, Tb (NO
3)
3, Er (NO
3)
3Or Tm (NO
3)
3In one or both.
Adopt above-mentioned alkaline earth ion solid solution titanate prescription and high-temperature atmosphere to burn till the present invention who constitutes into principal character, can be under the ion situation that to introduce charge defects that undopes, in fluorescent material matrix, introduce lattice distortion by the element substituting effect between alkaline earth ion, change rare-earth luminescent center ion chemical environment on every side, and regulate and control the matrix structure defective of fluorescent material, thereby obtain environmental protection type alkaline earth ion solid solution titanate fluorescent powder of high brightness and preparation method thereof in conjunction with some special preparation process conditions.The environmental protection type alkaline earth titanate fluorescent powder of the present invention's preparation has nontoxicity, and material behaviors such as high stability of material and good luminescent properties are a kind of phosphor material powders that has development prospect.As utilize the present invention to prepare to mix the praseodymium ion and make luminescence center ionic red alkaline earth ion solid solution titanate fluorescent powder, with research both at home and abroad at present with use electron-beam excitation Zn
1-xCd
xThe preparation method and the material property of S red fluorescence powder are compared, and have following characteristics:
1) with traditional Z n
1-xCd
xS fluorescent material is compared, and has the stability of material height, has no side effect, and the advantage of non-environmental-pollution is with a wide range of applications.
2) compare with the red alkaline earth titanate fluorescent powder that the conventional ion doping is burnt till, alkaline earth ion solid solution titanate fluorescent powder luminous intensity that atmosphere is burnt till improves an order of magnitude, can overcome phosphorescent substance matrix that mix a large amount of assisting ions and higher firing temperature bring and easily produce phase transformation, the material not problem of easy grinding of hardening.
3) material technology is stable, and can effectively control some trap kind and number in the luminous host by regulation and control atmosphere kind, the gentle flow condition of proportioning, and material luminous intensity and characteristic are regulated and optimized.
4), can develop and the fluorescent material new preparation process that a kind of ion of introducing charge defects of need not to mix just effectively improves such phosphor luminescence performance based on this type of alkaline earth ion solid solution formulating of recipe technology.
Embodiment
Embodiment 1
With chemical pure or analytical pure lime carbonate CaCO
3, Strontium carbonate powder SrCO
3, titanium dioxide TiO
2With praseodymium nitrate Pr (NO
3)
3Be raw material, by atomic ratio for (Ca: Sr): Ti: Pr is (0.8: 0.2): take by weighing each preparation of raw material admixtion at 1: 0.002, compound is put into the agate jar of 200ml, weight ratio by compound and agate ball grinding media is the agate ball grinding media that adding in 1: 1 has big or small proportioning, weight ratio by compound and deionized water is 1: 1 interpolation appropriate amount of deionized water, control rotating speed 200r/min ball milling 4h in planetary ball mill, the ball milling material is dried to make in 24 hours in 80 ℃ of baking ovens and is burnt till with compound pine dress powder sample, place in the plumbago crucible, be warming up to 1200 ℃ with 10 ℃/min, be incubated 3 hours, the cooling back obtains to burn till the fluorescence powder, by the weight ratio of burning till fluorescence powder and dehydrated alcohol is 1: 1.5 adding dehydrated alcohol, at rotating speed is ball milling mixing 24h in the 150r/min planetary ball mill, the ball milling material was dried 24 hours in 100 ℃ of baking ovens, promptly got (the Ca that burns till in the CO reducing atmosphere after the oven dry material sieves
0.8Sr
0.2) TiO
3: the 0.002Pr phosphor material powder.
Embodiment 2
With chemical pure or analytical pure lime carbonate CaCO
3, Strontium carbonate powder SrCO
3, titanium dioxide TiO
2With praseodymium nitrate Pr (NO
3)
3Be raw material, by atomic ratio for (Ca: Sr): Ti: Pr is (0.2: 0.8): take by weighing each preparation of raw material admixtion at 1: 0.002, compound is put into the agate jar of 200ml, weight ratio by compound and agate ball grinding media is the agate ball grinding media that adding in 1: 1 has big or small proportioning, weight ratio by compound and deionized water is 1: 1 interpolation appropriate amount of deionized water, the control rotating speed is 200r/min ball milling 4h in planetary ball mill, the ball milling material was dried 24 hours in 80 ℃ of baking ovens, the oven dry material is pressed into diameter 25mm at 150Mpa, the knobble of thickness 10～15mm obtains to burn till to use the compound compressing tablet.Compressing tablet is placed in the plumbago crucible, be warming up to 1250 ℃ with 10 ℃/min, be incubated 3 hours, the cooling back obtains to burn till the fluorescence powder, by the weight ratio of burning till fluorescence powder and dehydrated alcohol is 1: 1.5 adding dehydrated alcohol, at rotating speed is ball milling mixing 24h in the 150r/min planetary ball mill, and the ball milling material was dried 24 hours in 100 ℃ of baking ovens, promptly gets (the Ca that burns till in the CO reducing atmosphere after the oven dry material sieves
0.2Sr
0.8) TiO
3: the 0.002Pr fluorescent material.
Embodiment 3
With chemical pure or analytical pure Strontium carbonate powder SrCO
3, barium carbonate BaCO
3, titanium dioxide TiO
2With praseodymium nitrate Pr (NO
3)
3Be raw material, by atomic ratio for (Sr: Ba): Ti: Pr is (0.8: 0.2): take by weighing each preparation of raw material admixtion at 1: 0.002, compound is put into the agate jar of 200ml, weight ratio by compound and agate ball grinding media is the agate ball grinding media that adding in 1: 1 has big or small proportioning, weight ratio by compound and deionized water is 1: 1 interpolation appropriate amount of deionized water, the control rotating speed is 200r/min ball milling 4h in planetary ball mill, and the ball milling material was dried 24 hours in 80 ℃ of baking ovens.The oven dry material places in the plumbago crucible, be warming up to 1250 ℃ with 10 ℃/min, be incubated 4 hours, the cooling back obtains to burn till the fluorescence powder, by the weight ratio of burning till fluorescence powder and dehydrated alcohol is 1: 1.5 adding dehydrated alcohol, at rotating speed is ball milling mixing 24h in the 150r/min planetary ball mill, and the ball milling material was dried 24 hours in 100 ℃ of baking ovens, promptly gets (the Sr that burns till in the CO reducing atmosphere after the oven dry material sieves
0.8Ba
0.2) TiO
3: the 0.002Pr fluorescent material.
Embodiment 4
With chemical pure or analytical pure Strontium carbonate powder SrCO
3, barium carbonate BaCO
3, titanium dioxide TiO
2With praseodymium nitrate Pr (NO
3)
3Be raw material, by atomic ratio for (Sr: Ba): Ti: Pr is (0.2: 0.8): take by weighing each preparation of raw material admixtion at 1: 0.002, compound is put into the agate jar of 200ml, weight ratio by compound and agate ball grinding media is the agate ball grinding media that adding in 1: 1 has big or small proportioning, weight ratio by compound and deionized water is 1: 1 interpolation appropriate amount of deionized water, the control rotating speed is 200r/min ball milling 4h in planetary ball mill, and the ball milling material was dried 24 hours in 80 ℃ of baking ovens.The oven dry material places in the plumbago crucible, be warming up to 1300 ℃ with 10 ℃/min, be incubated 4 hours, the cooling back obtains to burn till the fluorescence powder, by the weight ratio of burning till fluorescence powder and dehydrated alcohol is 1: 1.5 adding dehydrated alcohol, at rotating speed is ball milling mixing 24h in the 150r/min planetary ball mill, and the ball milling material was dried 24 hours in 100 ℃ of baking ovens, promptly gets (the Sr that burns till in the CO reducing atmosphere after the oven dry material sieves
0.2Ba
0.8) TiO
3: the 0.002Pr fluorescent material.
Embodiment 5
With chemical pure or analytical pure lime carbonate CaCO
3, Strontium carbonate powder SrCO
3, barium carbonate BaCO
3, titanium dioxide TiO
2With praseodymium nitrate Pr (NO
3)
3Be raw material, by atomic ratio for (Ca: Sr: Ba): Ti: Pr is (0.1: 0.8: 0.1): take by weighing each preparation of raw material admixtion at 1: 0.002, compound is put into the agate jar of 200ml, weight ratio by compound and agate ball grinding media is the agate ball grinding media that adding in 1: 1 has big or small proportioning, weight ratio by compound and deionized water is 1: 1 interpolation appropriate amount of deionized water, the control rotating speed is 200r/min ball milling 4h in planetary ball mill, and the ball milling material was dried 24 hours in 80 ℃ of baking ovens.The oven dry material places in the plumbago crucible, be warming up to 1250 ℃ with 10 ℃/min, be incubated 4 hours, the cooling back obtains to burn till the fluorescence powder, by the weight ratio of burning till fluorescence powder and dehydrated alcohol is 1: 1.5 adding dehydrated alcohol, at rotating speed is ball milling mixing 24h in the 150r/min planetary ball mill, and the ball milling material was dried 24 hours in 100 ℃ of baking ovens, promptly gets (the Ca that burns till in the CO reducing atmosphere after the oven dry material sieves
0.1Sr
0.8Ba
0.1) TiO
3: the 0.002Pr fluorescent material.
Embodiment 6
With chemical pure or analytical pure lime carbonate CaCO
3, Strontium carbonate powder SrCO
3, barium carbonate BaCO
3, titanium dioxide TiO
2With praseodymium nitrate Pr (NO
3)
3Be raw material, by atomic ratio for (Ca: Sr: Ba): Ti: Pr is for (O.1: O.8: 0.1): take by weighing each preparation of raw material admixtion at 1: 0.002, compound is put into the agate jar of 200ml, weight ratio by compound and agate ball grinding media is the agate ball grinding media that adding in 1: 1 has big or small proportioning, weight ratio by compound and deionized water is 1: 1 interpolation appropriate amount of deionized water, the control rotating speed is 200r/min ball milling 4h in planetary ball mill, and the ball milling material was dried 24 hours in 80 ℃ of baking ovens.The oven dry material places in the alumina crucible, be warming up to 1250 ℃ with 10 ℃/min, be incubated 5 hours, the cooling back obtains to burn till the fluorescence powder, by the weight ratio of burning till fluorescence powder and dehydrated alcohol is 1: 1.5 adding dehydrated alcohol, at rotating speed is ball milling mixing 24h in the 150r/min planetary ball mill, and the ball milling material was dried 24 hours in 100 ℃ of baking ovens, promptly gets (the Ca that burns till in air atmosphere after the oven dry material sieves
0.1Sr
0.8Ba
0.1) TiO
3: the 0.002Pr fluorescent material.
Embodiment 7
With chemical pure or analytical pure lime carbonate CaCO
3, Strontium carbonate powder SrCO
3, barium carbonate BaCO
3, titanium dioxide TiO
2With praseodymium nitrate Pr (NO
3)
3Be raw material, by atomic ratio for (Ca: Sr: Ba): Ti: Pr is for (O.1: O.8: O.1): take by weighing each preparation of raw material admixtion at 1: 0.002, compound is put into the agate jar of 200ml, weight ratio by compound and agate ball grinding media is the agate ball grinding media that adding in 1: 1 has big or small proportioning, weight ratio by compound and deionized water is 1: 1 interpolation appropriate amount of deionized water, the control rotating speed is 200r/min ball milling 4h in planetary ball mill, and the ball milling material was dried 24 hours in 80 ℃ of baking ovens.The oven dry material places in the alumina crucible, puts into the corundum ceramic pipe of sealing, and feeding flow is the pure N of 100ml/min
2Gas, be warming up to 1250 ℃ with 10 ℃/min, being incubated 3 hours burns till, the cooling back obtains to burn till the fluorescence powder, by the weight ratio of burning till fluorescence powder and dehydrated alcohol is 1: 1.5 adding dehydrated alcohol, at rotating speed is ball milling mixing 24h in the 150r/min planetary ball mill, and the ball milling material was dried 24 hours in 100 ℃ of baking ovens, promptly gets at pure N after the oven dry material sieves
2(the Ca that reducing atmosphere burns till
0.1Sr
0.8Ba
0.1) TiO
3: the 0.002Pr fluorescent material.
Embodiment 8
With chemical pure or analytical pure lime carbonate CaCO
3, Strontium carbonate powder SrCO
3, barium carbonate BaCO
3, titanium dioxide TiO
2With praseodymium nitrate Pr (NO
3)
3Be raw material, by atomic ratio for (Ca: Sr: Ba): Ti: Pr is (0.1: 0.8: O.1): take by weighing each preparation of raw material admixtion at 1: 0.002, compound is put into the agate jar of 200ml, weight ratio by compound and agate ball grinding media is the agate ball grinding media that adding in 1: 1 has big or small proportioning, weight ratio by compound and deionized water is 1: 1 interpolation appropriate amount of deionized water, the control rotating speed is 200r/min ball milling 4h in planetary ball mill, and the ball milling material was dried 24 hours in 80 ℃ of baking ovens.The oven dry material places in the alumina crucible, puts into the corundum ceramic pipe of sealing, and feeding flow is the pure H of 100ml/min
2Gas, be warming up to 1250 ℃ with 10 ℃/min, being incubated 3 hours burns till, the cooling back obtains to burn till the fluorescence powder, by the weight ratio of burning till fluorescence powder and dehydrated alcohol is 1: 1.5 adding dehydrated alcohol, at rotating speed is ball milling mixing 24h in the 150r/min planetary ball mill, and the ball milling material was dried 24 hours in 100 ℃ of baking ovens, promptly gets at pure H after the oven dry material sieves
2(the Ca that reducing atmosphere burns till
0.1Sr
0.8Ba
0.1) TiO
3: the 0.002Pr fluorescent material.
Embodiment 9
With chemical pure or analytical pure lime carbonate CaCO
3, Strontium carbonate powder SrCO
3, barium carbonate BaCO
3, titanium dioxide TiO
2With praseodymium nitrate Pr (NO
3)
3Be raw material, by atomic ratio for (Ca: Sr: Ba): Ti: Pr is (0.1: 0.8: 0.1): take by weighing each preparation of raw material admixtion at 1: 0.002, compound is put into the agate jar of 200ml, weight ratio by compound and agate ball grinding media is the agate ball grinding media that adding in 1: 1 has big or small proportioning, weight ratio by compound and deionized water is 1: 1 interpolation appropriate amount of deionized water, the control rotating speed is 200r/min ball milling 4h in planetary ball mill, and the ball milling material was dried 24 hours in 80 ℃ of baking ovens.The oven dry material places in the alumina crucible, puts into the corundum ceramic pipe of sealing, and feeding flow is the N of 100ml/min
2: H
2=9: 1 gas mixture, be warming up to 1250 ℃ with 10 ℃/min, being incubated 3 hours burns till, the cooling back obtains to burn till the fluorescence powder, by the weight ratio of burning till fluorescence powder and dehydrated alcohol is 1: 1.5 adding dehydrated alcohol, at rotating speed is ball milling mixing 24h in the 150r/min planetary ball mill, and the ball milling material was dried 24 hours in 100 ℃ of baking ovens, promptly gets at N after the oven dry material sieves
2: H
2(the Ca that=9: 1 mixed atmosphere burns till
0.1Sr
0.8Ba
0.1) TiO
3: the 0.002Pr fluorescent material.
Embodiment 10
With chemical pure or analytical pure lime carbonate CaCO
3, Strontium carbonate powder SrCO
3, barium carbonate BaCO
3, titanium dioxide TiO
2With praseodymium nitrate Pr (NO
3)
3Be raw material, by atomic ratio for (Ca: Sr: Ba): Ti: Pr is (0.1: 0.8: 0.1): take by weighing each preparation of raw material admixtion at 1: 0.002, compound is put into the agate jar of 200ml, weight ratio by compound and agate ball grinding media is the agate ball grinding media that adding in 1: 1 has big or small proportioning, weight ratio by compound and deionized water is 1: 1 interpolation appropriate amount of deionized water, the control rotating speed is 200r/min ball milling 4h in planetary ball mill, and the ball milling material was dried 24 hours in 80 ℃ of baking ovens.The oven dry material places in the alumina crucible, puts into the corundum ceramic pipe of sealing, and feeding flow is the N of 100ml/min
2: H
2=1: 9 gas mixtures, be warming up to 1250 ℃ with 10 ℃/min, being incubated 3 hours burns till, the cooling back obtains to burn till the fluorescence powder, by the weight ratio of burning till fluorescence powder and dehydrated alcohol is 1: 1.5 adding dehydrated alcohol, at rotating speed is ball milling mixing 24h in the 150r/min planetary ball mill, and the ball milling material was dried 24 hours in 100 ℃ of baking ovens, promptly gets at N after the oven dry material sieves
2: H
2(the Ca that=1: 9 mixed atmospheres burn till
0.1Sr
0.8Ba
0.1) TiO
3: the 0.002Pr fluorescent material.
Embodiment 11
With chemical pure or analytical pure hexanaphthene, polyoxyethylene glycol Octyl Ether, praseodymium nitrate Pr (NO
3)
3, nitrocalcite Ca (NO
3)
3, strontium nitrate Sr (NO
3)
3, nitrate of baryta Ba (NO
3)
3, butyl (tetra) titanate and methyl ethyl diketone are raw material, by (Ca: Sr: Ba): Ti: Pr is (0.1: 0.8: 0.1): be preparation of raw material admixtion at 1: 0.002.Earlier with praseodymium nitrate Pr (NO
3)
3Be dissolved in the 50ml beaker, add appropriate amount of deionized water and be heated to dissolving fully, adjusting PH is 3～4, and solution Pr ionic concn is decided to be 1.0mol/L.Add the 100ml hexanaphthene in the erlenmeyer flask of 150ml, agitation condition adds 20ml surfactant polyethylene Octyl Ether down, adds then by proportioning and mixes 3ml Pr (NO
3)
3Solution, and Ca (NO
3)
3Solution, Sr (NO
3)
3Solution and Ba (NO
3)
3Solution, add again a spot of primary isoamyl alcohol to solution transparent till, continue to stir 30 minutes.Adding butyl (tetra) titanate is hydrolyzed and polycondensation, control its hydrolysis rate by the dissemination of water in the microemulsion, form the gel of homogeneous transparent at last, gel is placed 80 ℃ of dryings, dried xerogel takes out and grinds the wet-mixed material pine dress powder sample that obtains burning till usefulness, place in the alumina crucible, be warming up to 1150 ℃ with 10 ℃/min, be incubated 3 hours, the cooling back obtains to burn till the fluorescence powder, is 1: 1.5 adding dehydrated alcohol by the weight ratio of burning till fluorescence powder and dehydrated alcohol, is ball milling mixing 24h in the 150r/min planetary ball mill at rotating speed, the ball milling material was dried 24 hours in 100 ℃ of baking ovens, promptly got (the Ca that burns till in air atmosphere after the oven dry material sieves
0.1Sr
0.8Ba
0.1) TiO
3: the 0.002Pr fluorescent material.
Embodiment 12
With chemical pure or analytical pure hexanaphthene, polyoxyethylene glycol Octyl Ether, praseodymium nitrate Pr (NO
3)
3, nitrocalcite Ca (NO
3)
3, strontium nitrate Sr (NO
3)
3, nitrate of baryta Ba (NO
3)
3, butyl (tetra) titanate, aluminum nitrate Al (NO
3)
3With methyl ethyl diketone be raw material, by (Ca: Sr: Ba): Ti: Pr: Al be (0.1: 0.8: 0.1): be the preparation of raw material admixtion at 1: 0.002: 0.25.Earlier with praseodymium nitrate Pr (NO
3)
3Be dissolved in the 50ml beaker, add appropriate amount of deionized water and be heated to dissolving fully, adjusting PH is 3～4, and solution Pr ionic concn is decided to be 1.0mol/L.Add the 100ml hexanaphthene in the erlenmeyer flask of 150ml, agitation condition adds 20ml surfactant polyethylene Octyl Ether down, adds then by proportioning and mixes 3ml Pr (NO
3)
3Solution, and Ca (NO
3)
3Solution, Sr (NO
3)
3Solution, Ba (NO
3)
3Solution and Al (NO
3)
3Solution, add again a spot of primary isoamyl alcohol to solution transparent till, continue to stir 30 minutes.Adding butyl (tetra) titanate is hydrolyzed and polycondensation, control its hydrolysis rate by the dissemination of water in the microemulsion, form the gel of homogeneous transparent at last, gel is placed 80 ℃ of dryings, dried xerogel takes out to grind and obtains burning till the wet-mixed material of usefulness, be pressed into diameter 25mm at 150Mpa, the knobble of thickness 10～15mm, acquisition is burnt till and is used the compound compressing tablet, compressing tablet is placed in the alumina crucible, be warming up to 1100 ℃ with 10 ℃/min, be incubated 3 hours, the cooling back obtains to burn till the fluorescence powder, is 1: 1.5 adding dehydrated alcohol by the weight ratio of burning till fluorescence powder and dehydrated alcohol, is ball milling mixing 24h in the 150r/min planetary ball mill at rotating speed, the ball milling material was dried 24 hours in 100 ℃ of baking ovens, promptly got (the Ca that burns till in air atmosphere after the oven dry material sieves
0.1Sr
0.8Ba
0.1) TiO
3: 0.002Pr, 0.25Al fluorescent material.
Claims (3)
1. the preparation method of a high brilliancy environmental protection type alkaline earth ion solid solution titanate fluorescent powder is characterized in that: may further comprise the steps:
1) be (Ca according to the prescription composition formula
1-x-ySr
xBa
y) TiO
3: zRe, δ M, wherein 0≤x＜1.0,0≤y＜1.0 and 0＜x+y≤1.0,0＜z≤0.15,0≤δ≤0.4; Re is a Doped Rare Earth luminescence center ion, is praseodymium Pr; M is the supplementary doping element, is among boron, aluminium Al, gallium Ga, indium In, lithium Li, sodium Na or the potassium K one or more, burns till with solid phase batch mixing method or the preparation of wet-chemical reaction method and uses compound;
2) will burn till plumbago crucible or the corundum matter tube furnace of putting into high-temperature electric resistance furnace, favorable sealing property with compound, logical CO, N
2Or H
2In a kind of gas or its mixed gas, begin to be warming up to 900～1400 ℃ from room temperature, carried out sufficient pyroreaction in 1～6 hour in the firing temperature insulation of setting, after insulation finishes with 10 ℃/min, keep the firing atmosphere furnace cooling to room temperature, obtain to burn till the fluorescence powder;
3) be 1: 0.5～2.5 adding dehydrated alcohols by the weight ratio of burning till fluorescence powder and dehydrated alcohol, at rotating speed is that ball milling mixes 4～24h in 50～250r/min planetary ball mill, the ball milling material was dried 6～24 hours in 50～150 ℃ of baking ovens, after oven dry material sieves promptly.
2. preparation method according to claim 1 is characterized in that: described solid phase batch mixing method is: with alkaline earth carbonate, TiO
2, rare earth nitrate and supplementary doping element M compound be raw material, preparation raw material compound; Weight ratio by raw material compound and deionized water is 1: 0.5～1.5, adds deionized water, and ball milling mixes 2～12h in rotating speed 200r/min planetary ball mill, and the ball milling material was dried 10～48 hours in 50～150 ℃ of baking ovens, promptly got to burn till to use compound.
3. preparation method according to claim 1, it is characterized in that: described wet-chemical reaction method is: adopting compound, butyl (tetra) titanate and the rare earth nitrate of alkaline earth nitrate, supplementary doping element M is raw material, and is assistant chemical reagent with hexanaphthene, polyoxyethylene glycol Octyl Ether and methyl ethyl diketone; The rare earth nitrate raw material is added deionized water, and adjusting solution middle-weight rare earths ionic concn is 0.5～2.0mol/L, and pH value of solution is 2～6; Get 50～150ml hexanaphthene, under agitation condition, add 10～50ml surfactant polyethylene Octyl Ether, add nitric acid diluent then by proportioning blended rare earth nitrate solution 2～10ml, alkaline earth nitrate solution and supplementary doping element compound, add again primary isoamyl alcohol to solution transparent till, continue to stir 10～60 minutes; The butyl (tetra) titanate raw material that adds again by proportional quantity is hydrolyzed and polycondensation, control its hydrolysis rate by the dissemination of water in the microemulsion, form the gel main body of homogeneous transparent at last, it 50～250 ℃ of dryings, is promptly got to burn till after the exsiccant xerogel grinds and use compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610053079XA CN100572497C (en) | 2006-08-18 | 2006-08-18 | The preparation method of high brilliancy environmental protection type alkaline earth ion solid solution titanate fluorescent powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610053079XA CN100572497C (en) | 2006-08-18 | 2006-08-18 | The preparation method of high brilliancy environmental protection type alkaline earth ion solid solution titanate fluorescent powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1912049A CN1912049A (en) | 2007-02-14 |
| CN100572497C true CN100572497C (en) | 2009-12-23 |
Family
ID=37721115
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200610053079XA Expired - Fee Related CN100572497C (en) | 2006-08-18 | 2006-08-18 | The preparation method of high brilliancy environmental protection type alkaline earth ion solid solution titanate fluorescent powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100572497C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105529388A (en) * | 2016-01-25 | 2016-04-27 | 深圳市聚飞光电股份有限公司 | Implementation method for high-color-gamut white LED (Light Emitting Diode) using red phosphor |
| CN105552198A (en) * | 2016-01-25 | 2016-05-04 | 深圳市聚飞光电股份有限公司 | Implementation method for high-color-gamut white LED (Light Emitting Diode) using MxSr1-xTiO3:Eu2+,Mn2+ blue phosphor |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102912441B (en) * | 2011-08-05 | 2015-07-08 | 海洋王照明科技股份有限公司 | Cerium-terbium co-doped strontium titanate light-emitting film and preparation method thereof as well as organic electroluminescence device |
| JP2015519439A (en) * | 2012-05-08 | 2015-07-09 | ▲海▼洋王照明科技股▲ふん▼有限公司 | Titanate fluorescent material covering metal nanoparticles and method for producing the same |
| CN102690651A (en) * | 2012-06-05 | 2012-09-26 | 东华大学 | Method for preparing Zn2TiO4:Eu3+ fluorescent powder |
| CN104650875B (en) * | 2015-02-05 | 2017-01-04 | 浙江大学 | Er ions calcium titanate luminous nano granule and preparation method thereof |
| CN104861969A (en) * | 2015-05-20 | 2015-08-26 | 中国科学院新疆理化技术研究所 | Aluminum calcium titanate solid-solution type red phosphor and preparation method thereof |
| CN105623659B (en) * | 2016-01-25 | 2018-04-13 | 深圳市聚飞光电股份有限公司 | A kind of preparation method of LED titanate fluorescent powders |
| CN105754597B (en) * | 2016-03-31 | 2017-10-17 | 中南大学 | A kind of fluorescent RE powder titanate host material and preparation method thereof |
| CN116102055B (en) * | 2022-11-25 | 2024-08-23 | 中国科学院长春应用化学研究所 | Rare earth composite oxide colorant and preparation method thereof |
-
2006
- 2006-08-18 CN CNB200610053079XA patent/CN100572497C/en not_active Expired - Fee Related
Non-Patent Citations (6)
| Title |
|---|
| 溶胶-凝胶法合成Sr2MgSi2O7：EU2+,Dy3+长余辉发光材料. 姜洪义等.武汉理工大学学报，第27卷第7期. 2005 |
| 溶胶-凝胶法合成Sr2MgSi2O7：EU2+,Dy3+长余辉发光材料. 姜洪义等.武汉理工大学学报，第27卷第7期. 2005 * |
| 等价Ca、Sr离子固溶对CaTiO3：0.002Pr3＋发光特性的影响. 彭丽霞等.无机材料学报，第20卷第5期. 2005 |
| 等价Ca、Sr离子固溶对CaTiO3：0.002Pr3＋发光特性的影响. 彭丽霞等.无机材料学报，第20卷第5期. 2005 * |
| 补偿离子掺杂与烧成温度对SrTiO3：0.002Pr3＋材料的红色发光特性的影响. 洪樟连等.发光学报，第26卷第4期. 2005 |
| 补偿离子掺杂与烧成温度对SrTiO3：0.002Pr3＋材料的红色发光特性的影响. 洪樟连等.发光学报，第26卷第4期. 2005 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105529388A (en) * | 2016-01-25 | 2016-04-27 | 深圳市聚飞光电股份有限公司 | Implementation method for high-color-gamut white LED (Light Emitting Diode) using red phosphor |
| CN105552198A (en) * | 2016-01-25 | 2016-05-04 | 深圳市聚飞光电股份有限公司 | Implementation method for high-color-gamut white LED (Light Emitting Diode) using MxSr1-xTiO3:Eu2+,Mn2+ blue phosphor |
| CN105552198B (en) * | 2016-01-25 | 2018-04-13 | 深圳市聚飞光电股份有限公司 | One kind uses MxSr1‑xTiO3：Eu2+, Mn2+The high colour gamut white light LEDs implementation method of blue light fluorescent powder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1912049A (en) | 2007-02-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100572497C (en) | The preparation method of high brilliancy environmental protection type alkaline earth ion solid solution titanate fluorescent powder | |
| Zhang et al. | Photoluminescence and cathode-luminescence of Eu 3+-doped NaLnTiO 4 (Ln= Gd and Y) phosphors | |
| Geng et al. | Nanocrystalline CaYAlO 4: Tb 3+/Eu 3+ as promising phosphors for full-color field emission displays | |
| Li et al. | Tm 3+ and/or Dy 3+ doped LaOCl nanocrystalline phosphors for field emission displays | |
| CN100572496C (en) | High brightness red alkaline earth titanate fluorescent powder and reducing atmosphere treatment preparation method thereof thereof | |
| Taxak et al. | Synthesis, structural and optical properties of SrZrO3: Eu3+ phosphor | |
| Kang et al. | A novel blue-light excitable Pr3+ doped (Sr, Ba) LaMgTaO6 phosphor for plant growth lighting | |
| Liu et al. | Host-sensitized luminescence of Dy3+, Pr3+, Tb3+ in polycrystalline SrIn2O4 for field emission displays | |
| Yang et al. | Tunable blue-green color emission and energy transfer of Sr3NaSc (PO4) 3F: Eu2+, Tb3+ phosphors with near-UV broad band excited for white LEDs | |
| CN101177612A (en) | Praseodymium doped red long-afterglow luminescent material and preparation method thereof | |
| Yu et al. | Double-site Eu3+ occupation in the langbeinite-type phosphate phosphor toward adjustable emission for pc-WLEDs | |
| CN114686225A (en) | Near-infrared fluorescent powder and preparation method and application thereof | |
| Yu et al. | Enhanced photoluminescence of Ba2GdNbO6: Eu3+/Dy3+ phosphors by Li+ doping | |
| Wang et al. | Effects of heat-treatment on photoluminescence properties of MgAl2O4: Eu3+ red phosphors synthesized by a solution combustion method | |
| WO2013074158A1 (en) | Green and yellow aluminate phosphors | |
| CN101307228B (en) | Chlorine-aluminosilicate fluorescent powder and method for preparing same | |
| CN100529012C (en) | Red solid solution Sr-In-Ti phosphor and its preparing method | |
| Choi et al. | Effect of gadolinium incorporation on optical characteristics of YNbO4: Eu3+ phosphors for lamp applications | |
| US8765016B2 (en) | Green luminescent material of terbium doped gadolinium borate and preparing method thereof | |
| CN102428160B (en) | Green luminescent materials and their preparing methods | |
| CN110591711A (en) | Gallate red fluorescent powder for white light LED and preparation method thereof | |
| CN113549458B (en) | High-color-rendering trivalent Eu ion-doped red fluorescent material based on apatite structure and preparation method thereof | |
| CN104861973B (en) | Preparation method for green fluorescent powder applicable to white-light LED with lanthanum titanate serving as substrate and application of method | |
| CN102241978B (en) | Rare earth titanium tantalate-based luminescent material and preparation method thereof | |
| CN104031644A (en) | Molybdate up-conversion luminescent material, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20091223 Termination date: 20140818 |
|
| EXPY | Termination of patent right or utility model |