CN106947478B - A kind of long-afterglow material can be realized green emitting, preparation method and application - Google Patents
A kind of long-afterglow material can be realized green emitting, preparation method and application Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 21
- 230000005284 excitation Effects 0.000 claims abstract description 10
- 238000005286 illumination Methods 0.000 claims abstract description 5
- 239000010936 titanium Substances 0.000 claims description 40
- 239000011777 magnesium Substances 0.000 claims description 35
- 150000001875 compounds Chemical class 0.000 claims description 32
- 238000001354 calcination Methods 0.000 claims description 31
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 20
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 16
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 15
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 14
- 229910002651 NO3 Inorganic materials 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 13
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 12
- 239000000347 magnesium hydroxide Substances 0.000 claims description 12
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 12
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 11
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 10
- 229910052693 Europium Inorganic materials 0.000 claims description 9
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 8
- 239000000395 magnesium oxide Substances 0.000 claims description 8
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 7
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims description 7
- -1 europium ion Chemical class 0.000 claims description 7
- SULCVUWEGVSCPF-UHFFFAOYSA-L europium(2+);carbonate Chemical compound [Eu+2].[O-]C([O-])=O SULCVUWEGVSCPF-UHFFFAOYSA-L 0.000 claims description 7
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 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 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 6
- 229910001940 europium oxide Inorganic materials 0.000 claims description 6
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 6
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 6
- 239000001095 magnesium carbonate Substances 0.000 claims description 6
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 238000004020 luminiscence type Methods 0.000 abstract description 13
- 230000002688 persistence Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000003760 hair shine Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000003836 solid-state method Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 11
- 238000010586 diagram Methods 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 206010001497 Agitation Diseases 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 229910002538 Eu(NO3)3·6H2O Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000004645 aluminates Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000002285 radioactive effect Effects 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910003669 SrAl2O4 Inorganic materials 0.000 description 1
- 239000005084 Strontium aluminate Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000010893 electron trap Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 230000005524 hole trap Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7734—Aluminates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
- H01L2933/0008—Processes
- H01L2933/0033—Processes relating to semiconductor body packages
- H01L2933/0041—Processes relating to semiconductor body packages relating to wavelength conversion elements
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses a kind of long-afterglow material that can be realized green emitting, preparation method and application, the chemical general formula of the material is Mg2‑2xEu2xAl6Ti7O25, wherein x is Eu2+The mole percent of doping, 0.0001≤x≤0.5.The present invention uses high temperature solid-state method or chemical synthesis, and the material being prepared emits the green long afterglow near 550 nanometers under the excitation of ultraviolet light and shines.The chemical property of material is stablized, water-tolerant, luminous intensity is high, persistence is long, and the above-mentioned green long afterglow characteristics of luminescence having makes it possible to applied in the passive display of Noctilucent material, traffic safety instruction, dim light Emergency Light, display equipment etc. and the preparation for LED energy-saving illumination device；Preparation process of the invention is simple, synthesizes in air atmosphere, and production cost is low, no pollution to the environment, is convenient for large-scale production.
Description
Technical field
The present invention relates to a kind of long-afterglow materials that can be realized green emitting, preparation method and application, belong to inorganic hair
Luminescent material field.
Background technique
Long-afterglow material is a kind of photo-induced energy storage material, it generates light in the case where extraneous light source activation, absorbs simultaneously
Luminous energy simultaneously stores, and discharges outward in the form of light after stopping to its illumination, then by energy.Long-afterglow material has because of it
The features such as light storage, energy storage, energy conservation, is widely used in Noctilucent material, safety instruction, dim light Emergency Light and military science field
Deng.
For the system of long-afterglow material, long-afterglow material traditional in early days is concentrated mainly on ZnS, CaS sulfides
System, that there are stability is poor for the system, easily decomposes, the deficiencies of hygroscopicity is strong, afterglow performance is weak.Therefore, people are often at this
Radioactive element is added in class material to improve its afterglow property.But radioactive element seriously threatens the body and natural ring of people
Border, therefore the application of this long-afterglow material in practice is restricted.1996, Matsuzawa synthesized SrAl2O4:
Eu2+,Dy3+The long-afterglow material of green, mainly passes through Dy3+Non-equivalence displacement Sr2+Ion creates the electron trap of appropriate depth
With hole trap and there is dynamical luminous efficiency and superpower twilight sunset, subsequent aluminates system is widely studied and develops, at
For current main commercial long-afterglow material, has many advantages, such as after-glow brightness height, persistence is long, but its poor water resistance [X.D.L
ü, Mater.Chem.Phys.93 (2005) 526-530.], just easily undergo phase transition at 650 DEG C or more [M.Avdeev,
S.Yakovlev, A.A.Yaremchenko, V.V.Kharton, J.Solid State Chem.180, (2007) 3535.].For
Solve the problems, such as this, chemical property is stable, water resistance better than the silicate systems of aluminate becomes long-afterglow material in recent years
The hot spot of exploitation, but the system afterglow intensity and duration are still to be improved.
Summary of the invention
In view of the above-mentioned problems of the prior art, the purpose of the present invention is to provide a kind of chemical stability height, it will not
Generate the fluorescence realizing green long afterglow under ultraviolet excitation and shining polluted with radioactivity luminous intensity is high, persistence is long
Material, second object of the present invention be to provide a kind of preparation process it is simple, at low cost, environmentally friendly, convenient for industrialization
The preparation method of the long after glow luminous material of production；Third object of the present invention is to provide the application of above-mentioned fluorescent material.
To achieve the goals above, the technical solution adopted by the present invention is that: a kind of long afterglow can be realized green emitting
Material, the chemical general formula of the material are Mg2-2xEu2xAl6Ti7O25, wherein x is Eu2+The mole percent of doping, 0.0001≤
x≤0.5。
The present invention also provides the preparation methods of the above-mentioned long-afterglow material that can be realized green emitting, solid using high temperature
Xiang Fa includes the following steps:
(1) chemical formula Mg is pressed2-2xEu2xAl6Ti7O25The stoichiometric ratio of middle each element, wherein 0.0001≤x≤0.5, point
Also known as take containing magnesium ion Mg2+Compound, contain aluminium ion Al3+Compound, contain titanium ion Ti4+Compound, contain
Europium ion Eu3+Compound, grind and be uniformly mixed, obtain mixture；
(2) mixture that step (1) obtains is calcined in air atmosphere, calcination temperature is 350~850 DEG C, is forged
Burning the time is 3~9 hours；
(3) the mixture natural cooling for obtaining step (2), grind and after mixing, calcine, forge in a reducing atmosphere
Burning temperature is 950~1400 DEG C, and calcination time is 3~9 hours, naturally cools to room temperature to get fluorescent material is arrived.
Preferably, the calcination temperature of above-mentioned steps (2) is 500~700 DEG C, and calcination time is 5~7 hours.
Preferably, the calcination temperature of above-mentioned steps (3) is 1100~1250 DEG C, and calcination time is 5~7 hours.
In the above method, contain titanium ion Ti4+Compound be titanium dioxide TiO2；Contain aluminium ion Al3+Compound
For aluminium oxide Al2O3, aluminum nitrate Al (NO3)3·9H2O, aluminium carbonate Al2(CO3)3, aluminium hydroxide Al (OH)3One of；It is described
Contain magnesium ion Mg2+Compound be magnesia MgO, magnesium hydroxide Mg (OH)2, magnesium nitrate Mg (NO3)3·6H2O and alkali formula
Magnesium carbonate 4MgCO3·Mg(OH)2·5H2One of O；Described contains europium ion Eu3+Compound be europium oxide Eu2O3、
Europium nitrate Eu (NO3)3·6H2O, europium carbonate Eu2(CO3)3One of.
The present invention also provides another preparation methods of the above-mentioned long-afterglow material that can be realized green emitting, including
Following steps:
(1) chemical formula Mg is pressed2-2xEu2xAl6Ti7O25The stoichiometric ratio of middle each element, wherein 0.0005≤x≤0.5, claims
It takes containing magnesium ion Mg2+Compound, contain aluminium ion Al3+Compound and contain europium ion Eu3+Compound, be added
Suitable deionized water or dust technology stirring, until being completely dissolved；Then it weighs containing titanium ion Ti4+Compound, be added suitable
The glacial acetic acid solution of amount, heating stirring, until complete hydrolysis；Finally, the above several solns are mixed, stirred at 70-90 DEG C
Obtain uniform colloidal sol；
(2) above-mentioned colloidal sol is placed in an oven, temperature is 60 DEG C -100 DEG C, dries 12 hours, obtains xerogel；
(3) after natural cooling, presoma is taken out, is calcined in a reducing atmosphere, calcination temperature is 1000~1350 DEG C, calcining
Time is 3~10 hours, after natural cooling, and grinding uniformly obtains fluorescent material.
Above-mentioned contains titanium ion Ti4+Compound be butyl titanate C16H36O4Ti or tetraisopropyl titanate
C12H28O4Ti；Contain aluminium ion Al3+Compound be aluminum nitrate Al (NO3)3·9H2O, aluminium carbonate Al2(CO3)3, aluminium hydroxide
Al(OH)3One of；Described contains magnesium ion Mg2+Compound be magnesium hydroxide Mg (OH)2, magnesium nitrate Mg (NO3)3·
6H2O and basic magnesium carbonate 4MgCO3·Mg(OH)2·5H2One of O；Described contains europium ion Eu3+Compound be oxygen
Change europium Eu2O3, europium nitrate Eu (NO3)3·6H2O, europium carbonate Eu2(CO3)3One of.
The present invention also provides the applications of the above-mentioned long-afterglow material that can be realized green emitting, and the fluorescent powder is in purple
The outer lower green long afterglow that can emit near 550 nanometers of light excitation shines, and can be applied to Noctilucent material, traffic safety indicates, is weak
Light Emergency Light, the passive display of display equipment etc. and the preparation for LED energy-saving illumination device.
Compared with prior art, the advantages of technical solution of the present invention, is:
(1) fluorescent material of the invention is with Mg2Al6Ti7O25For matrix, chemical property is stablized, water-tolerant；Use Eu2+
As the centre of luminescence and Trapping Centers, under ultraviolet light, the green long afterglow near 550 nanometers can be emitted and shone, and
Material emission intensity is high, and persistence can achieve 20-60 hours；
(2) the fluffy easy grinding of product, "dead", the luminescent material of preparation is without secondary pollution, be it is a kind of green it is inorganic
Long after glow luminous material, it is easy to popularize；
(3) preparation process of the invention is simple, synthesizes in air atmosphere, and production cost is low, and no pollution to the environment is convenient for
Large-scale production；
Chemical property of the present invention is stablized, and the above-mentioned green long afterglow characteristics of luminescence having makes it possible to applied to noctilucence material
Material, traffic safety instruction, dim light Emergency Light, the passive display of display equipment etc. and the preparation for LED energy-saving illumination device
In.
Detailed description of the invention
Fig. 1 is that the embodiment of the present invention 1 prepares sample Mg1.998Eu0.002Al6Ti7O25X-ray powder diffraction pattern；
Fig. 2 is that the embodiment of the present invention 1 prepares sample Mg1.998Eu0.002Al6Ti7O25Hair under the excitation of 330 nano wave length light
Light spectrogram；
Fig. 3 is that the embodiment of the present invention 1 prepares sample Mg1.998Eu0.002Al6Ti7O25Decay of luminescence curve；
Fig. 4 is that the embodiment of the present invention 1 prepares sample Mg1.998Eu0.002Al6Ti7O25Scanning electron microscope diagram spectrum；
Fig. 5 is that the embodiment of the present invention 5 prepares sample Mg1.6Eu0.4Al6Ti7O25X-ray powder diffraction pattern；
Fig. 6 is that the embodiment of the present invention 5 prepares sample Mg1.6Eu0.4Al6Ti7O25Shining under the excitation of 330 nano wave length light
Spectrogram；
Fig. 7 is that the embodiment of the present invention 5 prepares sample Mg1.6Eu0.4Al6Ti7O25Decay of luminescence curve；
Fig. 8 is that the embodiment of the present invention 5 prepares sample Mg1.6Eu0.4Al6Ti7O25Scanning electron microscope diagram spectrum；
Specific embodiment
The invention will be further described with reference to the accompanying drawings and examples.
Embodiment 1
According to chemical formula Mg1.998Eu0.002Al6Ti7O25The stoichiometric ratio of middle each element claims magnesia MgO respectively:
0.805 gram, europium oxide Eu2O3: 0.004 gram, aluminium oxide Al2O3: 3.059 grams, titanium dioxide TiO2: 5.591 grams, in agate mortar
It is middle be added suitable acetone mixed grinding it is uniform after, precalcining is carried out in air atmosphere, calcined at 350 DEG C 3 hours it is cold with furnace
But after, sample is taken out by the raw material of precalcining and is sufficiently mixed grinding uniformly with identical method again, in a reducing atmosphere again
It calcines, is calcined 3 hours at 950 DEG C, be cooled to room temperature, be fully ground after taking-up and obtain sample.
It is the X-ray powder diffraction pattern that the present embodiment technical solution prepares sample referring to attached drawing 1；X-ray powder diffraction
Test result shows that prepared sample is single phase pure material.
It is the luminous light by the sample of the present embodiment technical solution preparation under the excitation of 330 nano wave length light referring to attached drawing 2
Spectrogram.Test result shows that sample can launch the green light near 550 nanometers under the excitation of ultraviolet light.
It is the decay of luminescence curve that the embodiment of the present invention 1 prepares sample, as can be seen from Figure more than this sample referring to attached drawing 3
Brightness die-away time can achieve 25 hours, can be used as long after glow luminous material.
It is the scanning electron microscope diagram that the embodiment of the present invention 1 prepares sample referring to attached drawing 4, it can be seen that prepared
Obtained sample particle is uniformly dispersed.
Embodiment 2
According to chemical formula Mg1.98Eu0.02Al6Ti7O25The stoichiometric ratio of middle each element weighs magnesium hydroxide Mg respectively
(OH)2: 0.577 gram, europium carbonate Eu2(CO3)3: 0.034 gram, aluminium carbonate Al2(CO3)3: 3.510 grams, titanium dioxide TiO2: 2.795
Gram, be added in the agate mortar suitable acetone mixed grinding it is uniform after, precalcining is carried out in air atmosphere, at 500 DEG C
After calcining furnace cooling in 5 hours, sample is taken out by the raw material of precalcining and is sufficiently mixed grinding uniformly with identical method again,
It is calcined again in reducing atmosphere, is calcined 5 hours at 1100 DEG C, be cooled to room temperature, be fully ground after taking-up and obtain sample.
The present embodiment technical solution prepare the X-ray powder diffraction pattern of sample, luminescent spectrum figure, decay of luminescence curve,
The sample prepared in scanning electron microscope diagram and embodiment 1 is consistent.
Embodiment 3
According to chemical formula Mg1.9Eu0.1Al6Ti7O25The stoichiometric ratio of middle each element weighs magnesium nitrate Mg respectively
(NO3)3·6H2O:2.436 grams, europium carbonate Eu2(CO3)3: 0.121 gram, aluminum nitrate Al (NO3)3·9H2O:5.627 grams, titanium dioxide
Titanium TiO2: 2.795 grams, be added in the agate mortar suitable acetone mixed grinding it is uniform after, carried out in air atmosphere pre-calcined
It burns, after calcining furnace cooling in 7 hours at 700 DEG C, takes out sample the raw material of precalcining is sufficiently mixed with identical method again
It closes grinding uniformly, calcines again in a reducing atmosphere, calcined 7 hours at 1250 DEG C, be cooled to room temperature, be fully ground i.e. after taking-up
Obtain sample.
The present embodiment technical solution prepare the X-ray powder diffraction pattern of sample, luminescent spectrum figure, decay of luminescence curve,
The sample prepared in scanning electron microscope diagram and embodiment 1 is consistent.
Embodiment 4
According to chemical formula Mg1.8Eu0.2Al6Ti7O25The stoichiometric ratio of middle each element, weighs basic magnesium carbonate respectively
4MgCO3·Mg(OH)2·5H2O:0.874 grams, europium oxide Eu2O3: 0.176 gram, aluminium hydroxide Al (OH)3: 2.340 grams, dioxy
Change titanium TiO2: 2.795 grams, be added in the agate mortar suitable acetone mixed grinding it is uniform after, carried out in air atmosphere pre-
Calcining after calcining furnace cooling in 9 hours at 850 DEG C, takes out sample and uses identical method abundant again the raw material of precalcining
Mixed grinding is uniform, calcines again in a reducing atmosphere, calcines 9 hours at 1400 DEG C, is cooled to room temperature, is fully ground after taking-up
Obtain sample.
The present embodiment technical solution prepare the X-ray powder diffraction pattern of sample, luminescent spectrum figure, decay of luminescence curve,
The sample prepared in scanning electron microscope diagram and embodiment 1 is consistent.
Embodiment 5
According to chemical formula Mg1.6Eu0.4Al6Ti7O25The stoichiometric ratio of middle each element weighs magnesia MgO respectively:
0.324 gram, europium oxide Eu2O3: 0.352 gram, aluminium oxide Al2O3: 1.529 grams, be dissolved in dilute nitric acid solution obtain it is uniform molten
Liquid.Weigh tetraisopropyl titanate C12H28O4Ti:11.911 grams, and suitable glacial acetic acid is added, heating stirring to complete hydrolysis obtains
To uniform solution.Both the above solution is mixed again, in 80 DEG C of magnetic agitations until obtaining colloidal sol.Obtained colloidal sol is placed
In baking oven, 75 DEG C dry 12 hours after obtain xerogel；Natural cooling is taken out presoma, is calcined in a reducing atmosphere, calcination temperature
It is 1000 DEG C, calcination time is 3 hours, takes out and is fully ground after cooling and obtains sample.
It is the X-ray powder diffraction pattern that the present embodiment technical solution prepares sample referring to attached drawing 5, the results show that being made
Sample crystallization it is good, no miscellaneous phase.
It is the luminous light by the sample of the present embodiment technical solution preparation under the excitation of 330 nano wave length light referring to attached drawing 6
Spectrogram.Test result shows that sample can launch the green light near 550 nanometers under the excitation of ultraviolet light, shows obtained
Material can be effectively by ultraviolet light switching emission green light.
It is the decay of luminescence curve that the embodiment of the present invention prepares sample referring to attached drawing 7, the decay of afterglow time can achieve 55
Hour, it can be deduced that this material is a kind of long after glow luminous material.
It is the scanning electron microscope diagram that the present embodiment technical solution prepares sample referring to attached drawing 8, the results show that using
Sample particle made from chemical method is more uniform, tiny, and average grain diameter is 0.27 micron.
Embodiment 6
According to chemical formula Mg1.4Eu0.6Al6Ti7O25The stoichiometric ratio of middle each element weighs magnesium hydroxide Mg respectively
(OH)2: 0.408 gram, europium nitrate Eu (NO3)3·6H2O:1.014 grams, aluminium hydroxide Al (OH)3: 2.340 grams, it is dissolved in dust technology
Uniform solution is obtained in solution.Weigh tetraisopropyl titanate C12H28O4Ti:9.948 grams, and suitable glacial acetic acid is added, it heats
Stirring to complete hydrolysis obtains uniform solution.Both the above solution is mixed into 70 DEG C of magnetic agitations until obtaining colloidal sol again；Most
Obtain at last colloidal sol place baking oven in, 60 DEG C dry 12 hours after obtain xerogel；Natural cooling takes out presoma, in also Primordial Qi
It is calcined in atmosphere, calcination temperature is 1150 DEG C, and calcination time is 5 hours, takes out and is fully ground after cooling and obtains sample.
The present embodiment technical solution prepare the X-ray powder diffraction pattern of sample, luminescent spectrum figure, decay of luminescence curve,
The sample prepared in scanning electron microscope diagram and embodiment 5 is consistent.
Embodiment 7
According to chemical formula Mg1.2Eu0.8Al6Ti7O25The stoichiometric ratio of middle each element weighs magnesium nitrate Mg respectively
(NO3)3·6H2O:0.615 grams, europium nitrate Eu (NO3)3·6H2O:0.541 grams, aluminum nitrate Al (NO3)3·9H2O:4.502 grams,
It is dissolved in deionized water and obtains uniform solution.Weigh butyl titanate C16H36O4Ti:4.764 grams, and suitable ice is added
Acetic acid, heating stirring to complete hydrolysis obtain uniform solution.Both the above solution is mixed into 80 DEG C of magnetic agitations until obtaining again
To colloidal sol；To obtain again colloidal sol place baking oven in, 100 DEG C dry 12 hours after obtain xerogel；Natural cooling takes out presoma,
It calcines in a reducing atmosphere, calcination temperature is 1250 DEG C, and calcination time is 8 hours, takes out and is fully ground after cooling and obtains
Sample.
The present embodiment technical solution prepare the X-ray powder diffraction pattern of sample, luminescent spectrum figure, decay of luminescence curve,
The sample prepared in scanning electron microscope diagram and embodiment 5 is consistent.
Embodiment 8
According to chemical formula MgEuAl6Ti7O25The stoichiometric ratio of middle each element weighs basic magnesium carbonate 4MgCO respectively3·
Mg(OH)2·5H2O:0.324 grams, europium carbonate Eu2(CO3)3: 0.807 gram, aluminium carbonate Al2(CO3)3: 2.340 grams, it is dissolved in dilute nitre
Uniform solution is obtained in acid solution.Weigh tetraisopropyl titanate C12H28O4Ti:6.632 grams, and suitable glacial acetic acid is added, add
Thermal agitation to complete hydrolysis obtains uniform solution；Both the above solution is mixed into 90 DEG C of magnetic agitations until obtaining colloidal sol again；
To obtain colloidal sol place baking oven in, 75 DEG C dry 12 hours after obtain xerogel；Natural cooling takes out presoma, in reducing atmosphere
Middle calcining, calcination temperature are 1350 DEG C, and calcination time is 10 hours, take out and are fully ground after cooling and obtain sample.
The present embodiment technical solution prepare the X-ray powder diffraction pattern of sample, luminescent spectrum figure, decay of luminescence curve,
The sample prepared in scanning electron microscope diagram and embodiment 5 is consistent.
Claims (8)
1. a kind of long-afterglow material that can be realized green emitting, it is characterised in that: the chemical general formula of the material is Mg2- 2xEu2xAl6Ti7O25, whereinxFor Eu2+The mole percent of doping, 0.0001≤x≤0.5.
2. a kind of preparation method for the long-afterglow material that can be realized green emitting as described in claim 1, solid using high temperature
Xiang Fa, which comprises the steps of:
(1) chemical formula Mg is pressed2-2xEu2xAl6Ti7O25The stoichiometric ratio of middle each element, wherein 0.0001≤x≤0.5, claims respectively
It takes containing magnesium ion Mg2+Compound, contain aluminium ion Al3+Compound, contain titanium ion Ti4+Compound, containing europium from
Sub- Eu3+Compound, grind and be uniformly mixed, obtain mixture；
(2) mixture that step (1) obtains is calcined in air atmosphere, calcination temperature is 350~850 DEG C, when calcining
Between be 3~9 hours；
(3) the mixture natural cooling for obtaining step (2), grinds and after mixing, calcines in a reducing atmosphere, calcining is warm
Degree is 950~1400 DEG C, and calcination time is 3~9 hours, naturally cools to room temperature to get fluorescent material is arrived.
3. a kind of preparation method of long-afterglow material that can be realized green emitting according to claim 2, feature exist
In: the calcination temperature of the step (2) is 500~700 DEG C, and calcination time is 5~7 hours.
4. a kind of preparation method of long-afterglow material that can be realized green emitting according to claim 2, feature exist
In: the calcination temperature of the step (3) is 1100~1250 DEG C, and calcination time is 5~7 hours.
5. a kind of preparation method of long-afterglow material that can be realized green emitting according to claim 2, feature exist
In: described contains titanium ion Ti4+Compound be titanium dioxide TiO2；Contain aluminium ion Al3+Compound be aluminium oxide
Al2O3, aluminum nitrate Al (NO3)3•9H2O, aluminium carbonate Al2(CO3)3, aluminium hydroxide Al (OH)3One of；It is described containing magnesium from
Sub- Mg2+Compound be magnesia MgO, magnesium hydroxide Mg (OH)2, magnesium nitrate Mg (NO3)2 •6H2O and basic magnesium carbonate
4MgCO3•Mg(OH)2•5H2One of O；Described contains europium ion Eu3+Compound be europium oxide Eu2O3, europium nitrate Eu
(NO3)3•6H2O, europium carbonate Eu2(CO3)3One of.
6. a kind of preparation method for the long-afterglow material that can be realized green emitting as described in claim 1, which is characterized in that
Include the following steps:
(1) chemical formula Mg is pressed2-2xEu2xAl6Ti7O25The stoichiometric ratio of middle each element, wherein 0.0005≤x≤0.5, weighs and contain
There is magnesium ion Mg2+Compound, contain aluminium ion Al3+Compound and contain europium ion Eu3+Compound, be added appropriate
Deionized water or dust technology stirring, until be completely dissolved；Then it weighs containing titanium ion Ti4+Compound, be added it is suitable
Glacial acetic acid solution, heating stirring, until complete hydrolysis；Finally, the above several solns are mixed, stirred to get at 70-90 DEG C
Uniform colloidal sol；
(2) above-mentioned colloidal sol is placed in an oven, temperature is 60 DEG C -100 DEG C, dries 12 hours, obtains xerogel；
(3) after natural cooling, presoma is taken out, is calcined in a reducing atmosphere, calcination temperature is 1000~1350 DEG C, calcination time
It is 3~10 hours, after natural cooling, grinding uniformly obtains fluorescent material.
7. the preparation method of the long-afterglow material according to claim 6 that can be realized green emitting, it is characterised in that: institute
That states contains titanium ion Ti4+Compound be butyl titanate C16H36O4Ti or tetraisopropyl titanate C12H28O4Ti；Containing aluminium from
Sub- Al3+Compound be aluminum nitrate Al (NO3)3•9H2O, aluminium carbonate Al2(CO3)3, aluminium hydroxide Al (OH)3One of；It is described
Contain magnesium ion Mg2+Compound be magnesium hydroxide Mg (OH)2, magnesium nitrate Mg (NO3)2 •6H2O and basic magnesium carbonate
4MgCO3•Mg(OH)2•5H2One of O；Described contains europium ion Eu3+Compound be europium oxide Eu2O3, europium nitrate Eu
(NO3)3•6H2O, europium carbonate Eu2(CO3)3One of.
8. a kind of application for the long-afterglow material that can be realized green emitting as described in claim 1, it is characterised in that: described
Fluorescent powder can emit the green long afterglow near 550 nanometers under ultraviolet excitation and shine, and can be applied to Noctilucent material, traffic peace
All referring to show, dim light Emergency Light, show equipment passive display and for the preparation of LED energy-saving illumination device.
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| CN105219387A (en) * | 2015-07-31 | 2016-01-06 | 江苏师范大学 | Metatitanic acid alkali red illuminating material of a kind of additive Mn and its preparation method and application |
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