CN106947478A - A kind of long-afterglow material that can realize green emitting, preparation method and application - Google Patents
A kind of long-afterglow material that can realize green emitting, preparation method and application Download PDFInfo
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- CN106947478A CN106947478A CN201710111757.1A CN201710111757A CN106947478A CN 106947478 A CN106947478 A CN 106947478A CN 201710111757 A CN201710111757 A CN 201710111757A CN 106947478 A CN106947478 A CN 106947478A
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- 239000000463 material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 21
- 238000005516 engineering process Methods 0.000 claims abstract description 7
- 238000005286 illumination Methods 0.000 claims abstract description 5
- 239000010936 titanium Substances 0.000 claims description 40
- 239000011777 magnesium Substances 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 32
- 238000001354 calcination Methods 0.000 claims description 30
- 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
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-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 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 13
- 229910002651 NO3 Inorganic materials 0.000 claims description 12
- 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
- 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
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000395 magnesium oxide Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229910021502 aluminium hydroxide Inorganic materials 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
- 239000000203 mixture Substances 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
- 229910002538 Eu(NO3)3·6H2O Inorganic materials 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
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-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 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 239000001095 magnesium carbonate Substances 0.000 claims description 5
- 229910000021 magnesium carbonate Inorganic materials 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
- 239000007787 solid Substances 0.000 claims description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 2
- 230000005284 excitation Effects 0.000 claims description 2
- GEIGXJHXQWKQAT-UHFFFAOYSA-N europium;nitric acid Chemical compound [Eu].O[N+]([O-])=O GEIGXJHXQWKQAT-UHFFFAOYSA-N 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 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
- 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 6
- 206010001497 Agitation Diseases 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000012456 homogeneous solution Substances 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
- 230000008901 benefit Effects 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
- 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
- 230000006872 improvement 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
- 230000035515 penetration Effects 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
Classifications
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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 realize 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 green long afterglow that the material prepared launches 550 nms under the exciting of ultraviolet light lights.The stable chemical nature of material, water-tolerant, luminous intensity is high, persistence is long, and the above-mentioned green long afterglow characteristics of luminescence possessed is so that it can apply in the passive display of Noctilucent material, traffic safety instruction, dim light Emergency Light, display device etc. and the preparation for LED energy-saving illumination devices；The preparation technology of the present invention is simple, is synthesized in air atmosphere, and production cost is low, environmentally safe, is easy to large-scale production.
Description
Technical field
The present invention relates to a kind of long-afterglow material that can realize green emitting, preparation method and application, belong to inorganic hair
Luminescent material field.
Background technology
Long-afterglow material is a kind of photo-induced energy storage material, and it produces light in the case of extraneous light source activation, is absorbed simultaneously
Luminous energy is simultaneously stored, and is outwards discharged in the form of light after stopping to its illumination, then by energy.Long-afterglow material has because of it
The features such as storage light, energy storage, energy-conservation, it 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, the deficiency such as the system existence and stability is poor, easily decompose, 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 replaces Sr2+Ion creates the electron trap of appropriate depth
With hole trap with dynamical luminous efficiency and superpower twilight sunset, subsequent aluminates system is widely studied and developed, into
For current main commercial long-afterglow material, persistence long the advantages of high with after-glow brightness, but its poor water resistance [X.D.L
ü, Mater.Chem.Phys.93 (2005) 526-530.], just easily undergo phase transition more than 650 DEG C [M.Avdeev,
S.Yakovlev, A.A.Yaremchenko, V.V.Kharton, J.Solid State Chem.180, (2007) 3535.].For
The problem is solved, stable chemical nature, water resistance turn into long-afterglow material in the last few years better than the silicate systems of aluminate
The focus of exploitation, but the system afterglow intensity and duration still have much room for improvement.
The content of the invention
The problem of existing for above-mentioned prior art, it is high it is an object of the invention to provide a kind of chemical stability, will not
Produce pollution and radioactivity luminous intensity height, the fluorescence for realizing that green long afterglow is luminous under ultraviolet excitation of persistence length
Material, second object of the present invention be a kind of simple preparation technology is provided, it is low cost, environmentally friendly, be easy to 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 these goals, the technical solution adopted by the present invention is：It is a kind of to realize the long afterglow of green emitting
Material, the chemical general formula of the material is Mg2-2xEu2xAl6Ti7O25, wherein x is Eu2+The mole percent of doping, 0.0001≤
x≤0.5。
It is solid using high temperature present invention also offers the preparation method of the above-mentioned long-afterglow material that can realize green emitting
Xiang Fa, comprises the following steps：
(1) chemical formula Mg is pressed2-2xEu2xAl6Ti7O25The stoichiometric proportion of middle each element, wherein 0.0001≤x≤0.5, point
Another name is taken containing magnesium ion Mg2+Compound, contain aluminium ion Al3+Compound, contain titanium ion Ti4+Compound, contain
Europium ion Eu3+Compound, grind and be well mixed, obtain mixture；
(2) mixture for obtaining step (1) is calcined in air atmosphere, and calcining heat is 350~850 DEG C, is forged
The burning time is 3~9 hours；
(3) the mixture natural cooling for obtaining step (2), after grinding and being well mixed, calcines in reducing atmosphere, forges
It is 950~1400 DEG C to burn temperature, and calcination time is 3~9 hours, naturally cools to room temperature, that is, obtains fluorescent material.
It is preferred that, the calcining heat of above-mentioned steps (2) is 500~700 DEG C, and calcination time is 5~7 hours.
It is preferred that, the calcining heat 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)3In one kind；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 kind in O；Described contains europium ion Eu3+Compound be europium oxide Eu2O3、
Europium nitrate Eu (NO3)3·6H2O, europium carbonate Eu2(CO3)3In one kind.
Present invention also offers another preparation method of the above-mentioned long-afterglow material that can realize green emitting, including
Following steps：
(1) chemical formula Mg is pressed2-2xEu2xAl6Ti7O25The stoichiometric proportion of middle each element, wherein 0.0005≤x≤0.5, claims
Take containing magnesium ion Mg2+Compound, contain aluminium ion Al3+Compound and contain europium ion Eu3+Compound, add
Appropriate deionized water or dust technology stirring, until being completely dissolved；Then weigh containing titanium ion Ti4+Compound, add suitable
The glacial acetic acid solution of amount, heating stirring, until complete hydrolysis；Finally, 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 reducing atmosphere, calcining heat is 1000~1350 DEG C, calcining
Time is 3~10 hours, after natural cooling, and grinding is uniform to obtain 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)3In one kind；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 kind in O；Described contains europium ion Eu3+Compound be oxygen
Change europium Eu2O3, europium nitrate Eu (NO3)3·6H2O, europium carbonate Eu2(CO3)3In one kind.
Present invention also offers the application of the above-mentioned long-afterglow material that can realize green emitting, the fluorescent material is in purple
Outer light excite the lower green long afterglow that can launch 550 nms light, can be applied to Noctilucent material, traffic safety indicate, it is weak
The passive display of light Emergency Light, display device etc. and the preparation for LED energy-saving illumination devices.
Compared with prior art, the advantage of technical solution of the present invention is：
(1) fluorescent material of the invention is with Mg2Al6Ti7O25For matrix, stable chemical nature, water-tolerant；Use Eu2+
As the centre of luminescence and Trapping Centers, under ultraviolet light, the green long afterglow that can launch 550 nms lights, and
Material emission intensity is high, and persistence can reach 20-60 hours；
(2) the fluffy easy grinding of product, "dead", the luminescent material non-secondary pollution of preparation, is a kind of green inorganic
Long after glow luminous material, is easy to penetration and promotion；
(3) preparation technology of the invention is simple, is synthesized in air atmosphere, and production cost is low, environmentally safe, is easy to
Large-scale production；
Stable chemical nature of the present invention, the above-mentioned green long afterglow characteristics of luminescence possessed is so that it can apply to noctilucence material
The passive display of material, traffic safety instruction, dim light Emergency Light, display device etc. and the preparation for LED energy-saving illumination devices
In.
Brief description of the drawings
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 in the case where 330 nano wave length light are excited
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 Mg1.6Eu0.4Al6Ti7O25It is luminous in the case where 330 nano wave length light are excited
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；
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 proportion 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 add appropriate acetone mixed grinding it is uniform after, carry out calcining at precalcining, 350 DEG C in air atmosphere 3 hours it is cold with stove
But after, take out sample and the raw material of precalcining is sufficiently mixed to grinding with identical method again uniformly, in reducing atmosphere again
Calcining, is calcined 3 hours at 950 DEG C, is cooled to be fully ground after room temperature, taking-up and is obtained sample.
It is the X-ray powder diffraction pattern that the present embodiment technical scheme prepares sample referring to accompanying drawing 1；X-ray powder diffraction
Test result shows that prepared sample is single phase pure material.
It is luminous light of the sample prepared by the present embodiment technical scheme in the case where 330 nano wave length light are excited referring to accompanying drawing 2
Spectrogram.Test result shows that sample can launch the green glow of 550 nms under the exciting 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 accompanying drawing 3
Brightness die-away time can reach 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, it can be seen that prepared referring to accompanying drawing 4
Obtained sample particle is uniformly dispersed.
Embodiment 2
According to chemical formula Mg1.98Eu0.02Al6Ti7O25The stoichiometric proportion 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, added in agate mortar appropriate acetone mixed grinding it is uniform after, precalcining is carried out in air atmosphere, at 500 DEG C
Calcine after furnace cooling in 5 hours, take out sample and the raw material of precalcining is sufficiently mixed to grinding with identical method again uniformly,
Calcined again in reducing atmosphere, calcined 5 hours at 1100 DEG C, be cooled to be fully ground after room temperature, taking-up and obtain sample.
The present embodiment technical scheme prepare the X-ray powder diffraction pattern of sample, luminescent spectrum figure, decay of luminescence curve,
Scanning electron microscope diagram is consistent with the sample prepared in embodiment 1.
Embodiment 3
According to chemical formula Mg1.9Eu0.1Al6Ti7O25The stoichiometric proportion 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, added in agate mortar appropriate acetone mixed grinding it is uniform after, carried out in air atmosphere pre-calcined
Burn, calcined at 700 DEG C after furnace cooling in 7 hours, take out sample and fully mix the raw material of precalcining with identical method again
Close grinding uniform, calcined again in reducing atmosphere, calcine 7 hours, be fully ground i.e. after being cooled to room temperature, taking-up at 1250 DEG C
Obtain sample.
The present embodiment technical scheme prepare the X-ray powder diffraction pattern of sample, luminescent spectrum figure, decay of luminescence curve,
Scanning electron microscope diagram is consistent with the sample prepared in embodiment 1.
Embodiment 4
According to chemical formula Mg1.8Eu0.2Al6Ti7O25The stoichiometric proportion of middle each element, weighs basic magnesium carbonate respectively
4MgCO3·Mg(OH)2·5H2O：0.874 gram, europium oxide Eu2O3：0.176 gram, aluminium hydroxide Al (OH)3：2.340 grams, dioxy
Change titanium TiO2：2.795 grams, added in agate mortar appropriate acetone mixed grinding it is uniform after, carried out in air atmosphere pre-
Calcining, is calcined after furnace cooling in 9 hours at 850 DEG C, takes out sample the raw material of precalcining is abundant with identical method again
Mixed grinding is uniform, is calcined again in reducing atmosphere, calcines 9 hours, is fully ground after being cooled to room temperature, taking-up at 1400 DEG C
Obtain sample.
The present embodiment technical scheme prepare the X-ray powder diffraction pattern of sample, luminescent spectrum figure, decay of luminescence curve,
Scanning electron microscope diagram is consistent with the sample prepared in embodiment 1.
Embodiment 5
According to chemical formula Mg1.6Eu0.4Al6Ti7O25The stoichiometric proportion of middle each element, weighs magnesia MgO respectively：
0.324 gram, europium oxide Eu2O3：0.352 gram, aluminium oxide Al2O3：1.529 grams, it is dissolved in dilute nitric acid solution and obtains uniform molten
Liquid.Weigh tetraisopropyl titanate C12H28O4Ti：11.911 grams, and appropriate glacial acetic acid is added, heating stirring to complete hydrolysis is obtained
To homogeneous 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, takes out presoma, is calcined in reducing atmosphere, calcining heat
For 1000 DEG C, calcination time is 3 hours, takes out and is fully ground after cooling and obtains sample.
Referring to accompanying drawing 5, it is the X-ray powder diffraction pattern that the present embodiment technical scheme prepares sample, as a result shows, is made
Sample crystallization it is good, no dephasign.
It is luminous light of the sample prepared by the present embodiment technical scheme in the case where 330 nano wave length light are excited referring to accompanying drawing 6
Spectrogram.Test result shows that sample can launch the green glow of 550 nms under the exciting of ultraviolet light, shows obtained
Material can be effectively by ultraviolet light switching emission green glow.
It is the decay of luminescence curve that the embodiment of the present invention prepares sample referring to accompanying drawing 7, the decay of afterglow time can reach 55
Hour, it can be deduced that this material is a kind of long after glow luminous material.
Referring to accompanying drawing 8, it is the scanning electron microscope diagram that the present embodiment technical scheme prepares sample, as a result shows, uses
Sample particle made from chemical method is more homogeneous, tiny, and its average grain diameter is 0.27 micron.
Embodiment 6
According to chemical formula Mg1.4Eu0.6Al6Ti7O25The stoichiometric proportion 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 appropriate glacial acetic acid is added, heat
Stirring obtains homogeneous solution to complete hydrolysis.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
Calcined in atmosphere, calcining heat 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 scheme prepare the X-ray powder diffraction pattern of sample, luminescent spectrum figure, decay of luminescence curve,
Scanning electron microscope diagram is consistent with the sample prepared in embodiment 5.
Embodiment 7
According to chemical formula Mg1.2Eu0.8Al6Ti7O25The stoichiometric proportion of middle each element, weighs magnesium nitrate Mg respectively
(NO3)3·6H2O：0.615 gram, europium nitrate Eu (NO3)3·6H2O：0.541 gram, 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 add appropriate ice
Acetic acid, heating stirring to complete hydrolysis obtains homogeneous 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,
Calcined in reducing atmosphere, calcining heat 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 scheme prepare the X-ray powder diffraction pattern of sample, luminescent spectrum figure, decay of luminescence curve,
Scanning electron microscope diagram is consistent with the sample prepared in embodiment 5.
Embodiment 8
According to chemical formula MgEuAl6Ti7O25The stoichiometric proportion of middle each element, weighs basic magnesium carbonate 4MgCO respectively3·
Mg(OH)2·5H2O：0.324 gram, 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 appropriate glacial acetic acid is added, plus
Thermal agitation to complete hydrolysis obtains homogeneous 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, calcining heat is 1350 DEG C, and calcination time is 10 hours, takes out and is fully ground after cooling and obtains sample.
The present embodiment technical scheme prepare the X-ray powder diffraction pattern of sample, luminescent spectrum figure, decay of luminescence curve,
Scanning electron microscope diagram is consistent with the sample prepared in embodiment 5.
Claims (8)
1. a kind of can realize the long-afterglow material of green emitting, it is characterised in that：The chemical general formula of the material is Mg2- 2xEu2xAl6Ti7O25, wherein x is Eu2+The mole percent of doping, 0.0001≤x≤0.5.
2. a kind of preparation method for the long-afterglow material that can realize green emitting as claimed in claim 1, solid using high temperature
Xiang Fa, it is characterised in that comprise the following steps：
(1) chemical formula Mg is pressed2-2xEu2xAl6Ti7O25The stoichiometric proportion of middle each element, wherein 0.0001≤x≤0.5, claims respectively
Take containing magnesium ion Mg2+Compound, contain aluminium ion Al3+Compound, contain titanium ion Ti4+Compound, containing europium from
Sub- Eu3+Compound, grind and be well mixed, obtain mixture；
(2) mixture for obtaining step (1) is calcined in air atmosphere, and calcining heat is 350~850 DEG C, during calcining
Between be 3~9 hours；
(3) the mixture natural cooling for obtaining step (2), after grinding and being well mixed, is calcined in reducing atmosphere, calcining temperature
Spend for 950~1400 DEG C, calcination time is 3~9 hours, naturally cools to room temperature, that is, obtains fluorescent material.
3. a kind of preparation method of long-afterglow material that can realize green emitting according to claims 2, its feature
It is：The calcining heat 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 realize green emitting according to claims 2, its feature
It is：The calcining heat 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 realize green emitting according to claims 2, its feature
It is：Described contains titanium ion Ti4+Compound be titanium dioxide TiO2；Contain aluminium ion Al3+Compound be aluminum oxide
Al2O3, aluminum nitrate Al (NO3)3·9H2O, aluminium carbonate Al2(CO3)3, aluminium hydroxide Al (OH)3In one kind；Described contains magnesium
ION Mg2+Compound be magnesia MgO, magnesium hydroxide Mg (OH)2, magnesium nitrate Mg (NO3)3·6H2O and basic magnesium carbonate
4MgCO3·Mg(OH)2·5H2One kind in O；Described contains europium ion Eu3+Compound be europium oxide Eu2O3, europium nitrate
Eu(NO3)3·6H2O, europium carbonate Eu2(CO3)3In one kind.
6. a kind of preparation method for the long-afterglow material that can realize green emitting as claimed in claim 1, it is characterised in that
Comprise the following steps：
(1) chemical formula Mg is pressed2-2xEu2xAl6Ti7O25The stoichiometric proportion 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, add appropriate
Deionized water or dust technology stirring, until be completely dissolved；Then weigh containing titanium ion Ti4+Compound, add appropriate
Glacial acetic acid solution, heating stirring, until complete hydrolysis；Finally, above several solns are mixed, stirs and obtain 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 reducing atmosphere, calcining heat is 1000~1350 DEG C, calcination time
For 3~10 hours, after natural cooling, grinding is uniform to obtain fluorescent material.
7. the preparation method in the long-afterglow material that can realize green emitting according to claims 6, its feature exists
In：Described contains titanium ion Ti4+Compound be butyl titanate C16H36O4Ti or tetraisopropyl titanate C12H28O4Ti；Contain
There is aluminium ion Al3+Compound be aluminum nitrate Al (NO3)3·9H2O, aluminium carbonate Al2(CO3)3, aluminium hydroxide Al (OH)3In one
Kind；Described contains magnesium ion Mg2+Compound be magnesium hydroxide Mg (OH)2, magnesium nitrate Mg (NO3)3·6H2O and basic carbonate
Magnesium 4MgCO3·Mg(OH)2·5H2One kind in O；Described contains europium ion Eu3+Compound be europium oxide Eu2O3, nitric acid
Europium Eu (NO3)3·6H2O, europium carbonate Eu2(CO3)3In one kind.
8. a kind of application for the long-afterglow material that can realize green emitting as claimed in claim 1, it is characterised in that：It is described
The green long afterglow that fluorescent material can launch 550 nms under ultraviolet excitation lights, and can be applied to Noctilucent material, traffic peace
All referring to showing, dim light Emergency Light, the passive display of display device etc. and the preparation for LED energy-saving illumination devices.
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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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