CN106701072A - Europium-doped calcium titanate nano cube fluorescent powder and preparation method thereof - Google Patents
Europium-doped calcium titanate nano cube fluorescent powder and preparation method thereof Download PDFInfo
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- CN106701072A CN106701072A CN201611196223.5A CN201611196223A CN106701072A CN 106701072 A CN106701072 A CN 106701072A CN 201611196223 A CN201611196223 A CN 201611196223A CN 106701072 A CN106701072 A CN 106701072A
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- europium
- water
- doped calcium
- calcium titanate
- ethanol
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- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000843 powder Substances 0.000 title abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 108
- 239000003513 alkali Substances 0.000 claims abstract description 37
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000725 suspension Substances 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000007900 aqueous suspension Substances 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- 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 abstract description 18
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000004687 hexahydrates Chemical class 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 68
- 239000007787 solid Substances 0.000 claims description 34
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- 238000004140 cleaning Methods 0.000 claims description 20
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 17
- 238000005119 centrifugation Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000012153 distilled water Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- 229910001948 sodium oxide Inorganic materials 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 235000019441 ethanol Nutrition 0.000 abstract 5
- 239000007864 aqueous solution Substances 0.000 abstract 2
- 239000002243 precursor Substances 0.000 abstract 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000001816 cooling Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 238000002242 deionisation method Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910010252 TiO3 Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- -1 rare earth ion Chemical class 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 229910002971 CaTiO3 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910002538 Eu(NO3)3·6H2O Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- ZBGLGVFYHCSILI-UHFFFAOYSA-N acetic acid;europium Chemical compound [Eu].CC(O)=O ZBGLGVFYHCSILI-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- KPVUHKHVGKSEPB-UHFFFAOYSA-N calcium europium Chemical compound [Ca][Eu] KPVUHKHVGKSEPB-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 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 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
- C09K11/7729—Chalcogenides
- C09K11/7731—Chalcogenides with alkaline earth metals
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses europium-doped calcium titanate nano cube fluorescent powder and a preparation method thereof. The cube fluorescent powder is cubic europium-doped calcium titanate with the edge length of 245 to 815 nm. The preparation method comprises the following steps: mixing butyl titanate, ethyl alcohol and water to form butyl titanate ethyl alcohol aqueous suspension, mixing a calcium nitrate tetrahydrate, europium nitrate (III) hexahydrate and ethyl alcohol to obtain a mixed solution, then mixing alkali, ethyl alcohol and water to obtain an alkaline ethyl alcohol aqueous solution, dropwise adding the mixed solution into the butyl titanate ethyl alcohol aqueous suspension in sequence, carrying out stirring to obtain middle suspension, dropwse adding the alkaline ethyl alcohol aqueous solution into the middle suspension, then carrying out stirring to obtain precursor white suspension, finally placing the precursor white suspension at 180 to 220 DEG C for closed reaction, and carrying out solid-liquid separation, washing and drying on cooled reaction liquid to obtain a target product. The stimulated lighting performance of the europium-doped calcium titanate nano cube fluorescent powder is effectively improved, and the europium-doped calcium titanate nano cube fluorescent powder can be easily and widely commercially used as a white LED fluorescence material.
Description
Technical field
The present invention relates to a kind of square fluorescent material and preparation method, especially a kind of europium-doped calcium titanate nano square fluorescence
Powder and preparation method thereof.
Background technology
White light LEDs are described as the green illumination light source of a new generation, have many relative to traditional incandescent lamp, fluorescent lamp etc.
Advantage, such as caloric value are small, energy saving, luminous efficiency high, long lifespan, small volume, environmental protection.Except applying in lighting field,
White light LEDs application field is also including LCD backlight --- automobile, sound equipment instrument, cell phone back tabula rasa etc. and traffic lights, mark
Will lamp, information display screen etc..One of major way that white light LEDs are realized is combined with fluorescent material by single LED chip
After send white light, fluorescent material section or after all absorbing the light of the short wavelength that LED sends sends visible ray, is finally combined
Form white light.Calcium titanate with excellent optics, electricity, calorifics and mechanical performance, physical and chemical performance at normal temperatures is non-
It is often stable；When as host material, after rare earth ion is mixed into Ga acquisition fluorescent material, it has energy transmission very high
Efficiency, is that a kind of potentially can be used for the fluorescent material of white light LEDs.In order to obtain this fluorescent material, made some has people
The trial and effort of benefit, such as entitled " Structural and photoluminescence studies of red
emitting CaTiO3:Eu3+Perovskite nanophosphors for lighting applications. ", J
Mater Sci-Mater El 2016,27 (10), 10371-10381 (" the Ca-Ti ore type CaTiO based on illumination application3:Eu3+
Structure and the luminescent properties research of emitting red light nano-phosphor ",《Electronic material science》The 10th phase 10371 of volume 27 in 2016
Page~10381) article.The product referred in this article is europium-doped calcium titanate, and its chemical general formula is Ca1-xTiO3:xEu(0.01
≤ x≤0.10), pattern be Size Distribution in the irregular graininess of 70~170nm, it most preferably excites peak position in 397nm, most
Good transmitting peak position is 619nm；Preparation method is for first by isopropyl titanate, calcium carbonate, acetic acid, water and acetic acid europium by chemical coprecipitation
Shallow lake method obtains sediment, then by the sediment after cleaning after drying, 1000 DEG C of heat treatment synthetic product.Though this product can
As being excited to send feux rouges, for sending the fluorescent material of white light after being combined with the light that LED chip sends, but with its preparation side
Method all has weak point, and first, the purity of product is not high, the dephasign containing carbonate, and the presence of dephasign can typically influence
Transmission of the energy in parent lattice to its fluorescence property so that have more significant inhibitory action；Secondly, Size Distribution is uneven
The defect on one granular disintegration surface is more, and the perfection of lattice of product is bad, also its luminous efficiency can be produced certain
Influence；Again, preparation method has the temperature of heat treatment too high in addition to it can not obtain the product that purity is high, lattice is complete, also
And cause the defect of power consumption.
The content of the invention
The technical problem to be solved in the present invention is to overcome weak point of the prior art, there is provided a kind of purity is high, lattice
Complete europium-doped calcium titanate nano square fluorescent material.
The invention solves the problems that another technical problem to provide a kind of above-mentioned europium-doped calcium titanate nano square fluorescent material
Preparation method.
Be to solve technical problem of the invention, the technical scheme for being used for：Europium-doped calcium titanate nano square fluorescent material
It is made up of europium-doped calcium titanate nano particle, particularly,
The europium-doped calcium titanate nano particle is square block, and the square length of side of the square block europium-doped calcium titanate is
245~815nm.
Be to solve another technical problem of the invention, another technical scheme for being used for：Above-mentioned europium doped titanic acid
The preparation method of calcium nano square fluorescent material includes that solvent-thermal method, particularly key step are as follows：
Step 1, is first 0.62~0.82 according to the volume ratio of butyl titanate (C16H36O4Ti), second alcohol and water:13~17:
1~8 ratio, after butyl titanate and ethanol stirring are mixed, is added dropwise over water and stirs the second for forming butyl titanate thereto
Alcohol aqueous suspension, according still further to calcium nitrate tetrahydrate (Ca (NO3)2·4H2O), europium nitrate (III) hexahydrate (Eu (NO3)3·
6H2O) and ethanol weight ratio be 0.34~0.54：0.052~0.072：10~14 ratio mixes three, is mixed
Solution；
Step 2, is first 0.4~0.6 according to the weight ratio of alkali, second alcohol and water：10.2~12.2：1 ratio mixes three
Close, obtain the ethanol water of alkali, according still further to the ethanol water of the ethanol aqueous suspension, mixed solution and alkali of butyl titanate
Volume ratio is 1~1.4：0.8~1.2：0.8~1.2 ratio, mixed solution is added dropwise over the ethanol water of butyl titanate successively
After in suspension, at least 1.5h is stirred, obtain middle suspension, the ethanol water of alkali is added dropwise in middle suspension
Afterwards, at least 2h is stirred, forerunner's white suspension is obtained；
Step 3, confined reaction at least 6h at forerunner's white suspension first is placed in into 180~220 DEG C, obtains reaction solution, then
Carry out separation of solid and liquid, washing and dry treatment successively to the reaction solution after cooling, europium-doped calcium titanate nano square is obtained glimmering
Light powder.
As the further improvement of the preparation method of europium-doped calcium titanate nano square fluorescent material：
Preferably, water is deionized water, or distilled water.
Preferably, alkali is NaOH, or potassium hydroxide.
Preferably, separation of solid and liquid is processed as centrifugation, and its rotating speed is 5000~8000r/min, the time is 2~6min.
Preferably, carrying out washing treatment is to carry out the alternating of 3~5 times to isolated solid using ethanol and deionized water
Cleaning, it is centrifugation that solid is separated during cleaning.
Preferably, dried process is 5~7h of baking at the solid after cleaning is placed in into 50~70 DEG C.
Beneficial effect relative to prior art is：
First, carrying out table using ESEM, X-ray diffractometer and XRF respectively to obtained purpose product
Levy, from its result, the pattern of purpose product is square block, and the length of side of its square is 245~815nm；Composition adulterates for europium
Calcium titanate, its chemical general formula is Ca1-xTiO3:xEu(0.01≤x≤0.11)；Optimal excitation peak is located at 395nm, optimal emission peak
Positioned at 615nm.This purpose product being made up of square block europium-doped calcium titanate, both because europium-doped calcium titanate is square block,
And make its not only good crystallinity, surface it is smooth, and lattice defect is few, pole beneficial to fluorescence intensity enhancing, while also there is dispersion
Property it is good, be difficult reunite advantage；Again because of the excited fluorescence speciality of europium-doped calcium titanate itself；Due also in europium-doped calcium titanate not
Containing dephasign；So that the stimulated luminescence performance of purpose product has obtained effective lifting.
Second, preparation method science, efficiently.The purpose product that purity is high, lattice is complete has not only been obtained --- europium adulterates
Calcium titanate nano square fluorescent material；Also make it have stimulated luminescence performance higher；More there is the purpose product for obtaining to be only
The europium-doped calcium titanate of pure phase, and the temperature of reaction is low --- energy-conservation, the characteristics of so as to be easy to industrial-scale production；And then
Purpose product is set to be extremely easy to widely be commercialized the fluorescent material as white light LEDs.
Brief description of the drawings
Fig. 1 is one of result for being characterized using ESEM (SEM) to purpose product obtained in preparation method.SEM
Image shows that purpose product is the good square block of dispersiveness.
Fig. 2 is one of result for being characterized using X-ray diffraction (XRD) instrument to obtained purpose product.Wherein, XRD
XRD standard spectral line, spectral line that upper curve be purpose product of the bottom curve of spectrogram for orthorhombic phase calcium titanate；The XRD spectra
Show purpose product for orthorhombic phase calcium titanate, there is no impurities phase, and the doping of rare earth ion is not produced significantly to crystalline phase
Influence.
Fig. 3 is one of result for being characterized using steady-state lifetime XRF to obtained purpose product.Fluorescence light
Spectral line in spectrogram shows, the maximum excitation wavelength of purpose product is located at 395nm, optimal launch wavelength at 615nm, by
It understands that purpose product can efficiently be excited by purple light and send feux rouges.Understood with reference to Fig. 2, the composition of purpose product is changed for it
Formula is Ca1-xTiO3:The europium-doped calcium titanate of xEu (0.01≤x≤0.11).
Specific embodiment
Preferred embodiment of the invention is described in further detail below in conjunction with the accompanying drawings.
Bought from market first or be voluntarily obtained：
Butyl titanate；
Ethanol；
As the deionized water and distilled water of water；
Calcium nitrate tetrahydrate；
Europium nitrate (III) hexahydrate；
As the NaOH and potassium hydroxide of alkali.
Then,
Embodiment 1
What is prepared concretely comprises the following steps：
Step 1, is first 0.62 according to the volume ratio of butyl titanate, second alcohol and water:17:1 ratio, by butyl titanate and second
After alcohol stirring mixing, water is added dropwise over thereto and the ethanol aqueous suspension for forming butyl titanate is stirred；Wherein, water is deionization
Water (or distilled water).Weight ratio according still further to calcium nitrate tetrahydrate, europium nitrate (III) hexahydrate and ethanol is 0.34：
0.072：10 ratio mixes three, obtains mixed solution.
Step 2, is first 0.4 according to the weight ratio of alkali, second alcohol and water：12.2：1 ratio mixes three；Wherein, water is
Deionized water (or distilled water), alkali is NaOH (or potassium hydroxide), obtains the ethanol water of alkali.According still further to butyl titanate
Ethanol aqueous suspension, mixed solution and alkali ethanol water volume ratio be 1：1.2：0.8 ratio, will mix molten successively
After liquid is added dropwise in the ethanol aqueous suspension of butyl titanate, 1.5h is stirred, middle suspension is obtained, by the ethanol water of alkali
After being added dropwise in middle suspension, 2h is stirred, obtain forerunner's white suspension.
Step 3, confined reaction 24h at forerunner's white suspension first is placed in into 180 DEG C, obtains reaction solution.Again to cooling after
Reaction solution carry out successively separation of solid and liquid, washing and dry treatment；Wherein, separation of solid and liquid is processed as centrifugation, its rotating speed
For 5000r/min, time are 6min, carrying out washing treatment is isolated solid to be carried out 3 times using ethanol and deionized water
Alternating cleaning, during cleaning separate solid be centrifugation, dried process be at the solid after cleaning is placed in into 50 DEG C dry
7h.It is obtained and is similar to shown in Fig. 1, and the europium-doped calcium titanate nano square fluorescent material as shown in the curve in Fig. 2 and Fig. 3.
Embodiment 2
What is prepared concretely comprises the following steps：
Step 1, is first 0.67 according to the volume ratio of butyl titanate, second alcohol and water:16:3 ratio, by butyl titanate and second
After alcohol stirring mixing, water is added dropwise over thereto and the ethanol aqueous suspension for forming butyl titanate is stirred；Wherein, water is deionization
Water (or distilled water).Weight ratio according still further to calcium nitrate tetrahydrate, europium nitrate (III) hexahydrate and ethanol is 0.39：
0.067：11 ratio mixes three, obtains mixed solution.
Step 2, is first 0.45 according to the weight ratio of alkali, second alcohol and water：11.7：1 ratio mixes three；Wherein, water
It is deionized water (or distilled water) that alkali is NaOH (or potassium hydroxide), obtains the ethanol water of alkali.According still further to metatitanic acid fourth
The volume ratio of the ethanol water of the ethanol aqueous suspension, mixed solution and alkali of ester is 1.1：1.1：0.9 ratio, successively will be mixed
After conjunction solution is added dropwise in the ethanol aqueous suspension of butyl titanate, 2h is stirred, obtain middle suspension, the ethanol of alkali is water-soluble
After liquid is added dropwise in middle suspension, 2.5h is stirred, obtain forerunner's white suspension.
Step 3, confined reaction 20h at forerunner's white suspension first is placed in into 190 DEG C, obtains reaction solution.Again to cooling after
Reaction solution carry out successively separation of solid and liquid, washing and dry treatment；Wherein, separation of solid and liquid is processed as centrifugation, its rotating speed
For 6000r/min, time are 5min, carrying out washing treatment is isolated solid to be carried out 3 times using ethanol and deionized water
Alternating cleaning, during cleaning separate solid be centrifugation, dried process be at the solid after cleaning is placed in into 55 DEG C dry
6.5h.It is obtained and is similar to shown in Fig. 1, and the europium-doped calcium titanate nano square fluorescence as shown in the curve in Fig. 2 and Fig. 3
Powder.
Embodiment 3
What is prepared concretely comprises the following steps：
Step 1, is first 0.72 according to the volume ratio of butyl titanate, second alcohol and water:15:5 ratio, by butyl titanate and second
After alcohol stirring mixing, water is added dropwise over thereto and the ethanol aqueous suspension for forming butyl titanate is stirred；Wherein, water is deionization
Water (or distilled water).Weight ratio according still further to calcium nitrate tetrahydrate, europium nitrate (III) hexahydrate and ethanol is 0.44：
0.062：12 ratio mixes three, obtains mixed solution.
Step 2, is first 0.5 according to the weight ratio of alkali, second alcohol and water：11.2：1 ratio mixes three；Wherein, water is
Deionized water (or distilled water), alkali is NaOH (or potassium hydroxide), obtains the ethanol water of alkali.According still further to butyl titanate
Ethanol aqueous suspension, mixed solution and alkali ethanol water volume ratio be 1.2：1：1 ratio, successively by mixed solution
After being added dropwise in the ethanol aqueous suspension of butyl titanate, stir 2.5h, obtain middle suspension, by the ethanol water of alkali by
After being added dropwise in middle suspension, 3h is stirred, obtain forerunner's white suspension.
Step 3, confined reaction 15h at forerunner's white suspension first is placed in into 200 DEG C, obtains reaction solution.Again to cooling after
Reaction solution carry out successively separation of solid and liquid, washing and dry treatment；Wherein, separation of solid and liquid is processed as centrifugation, its rotating speed
For 6500r/min, time are 4min, carrying out washing treatment is isolated solid to be carried out 4 times using ethanol and deionized water
Alternating cleaning, during cleaning separate solid be centrifugation, dried process be at the solid after cleaning is placed in into 60 DEG C dry
6h.It is obtained as shown in figure 1, and the europium-doped calcium titanate nano square fluorescent material as shown in the curve in Fig. 2 and Fig. 3.
Embodiment 4
What is prepared concretely comprises the following steps：
Step 1, is first 0.77 according to the volume ratio of butyl titanate, second alcohol and water:14:7 ratio, by butyl titanate and second
After alcohol stirring mixing, water is added dropwise over thereto and the ethanol aqueous suspension for forming butyl titanate is stirred；Wherein, water is deionization
Water (or distilled water).Weight ratio according still further to calcium nitrate tetrahydrate, europium nitrate (III) hexahydrate and ethanol is 0.49：
0.057：13 ratio mixes three, obtains mixed solution.
Step 2, is first 0.55 according to the weight ratio of alkali, second alcohol and water：10.7：1 ratio mixes three；Wherein, water
It is deionized water (or distilled water) that alkali is NaOH (or potassium hydroxide), obtains the ethanol water of alkali.According still further to metatitanic acid fourth
The volume ratio of the ethanol water of the ethanol aqueous suspension, mixed solution and alkali of ester is 1.3：0.9：1.1 ratio, successively will be mixed
After conjunction solution is added dropwise in the ethanol aqueous suspension of butyl titanate, 3h is stirred, obtain middle suspension, the ethanol of alkali is water-soluble
After liquid is added dropwise in middle suspension, 3.5h is stirred, obtain forerunner's white suspension.
Step 3, confined reaction 10h at forerunner's white suspension first is placed in into 210 DEG C, obtains reaction solution.Again to cooling after
Reaction solution carry out successively separation of solid and liquid, washing and dry treatment；Wherein, separation of solid and liquid is processed as centrifugation, its rotating speed
For 7000r/min, time are 3min, carrying out washing treatment is isolated solid to be carried out 4 times using ethanol and deionized water
Alternating cleaning, during cleaning separate solid be centrifugation, dried process be at the solid after cleaning is placed in into 65 DEG C dry
5.5h.It is obtained and is similar to shown in Fig. 1, and the europium-doped calcium titanate nano square fluorescence as shown in the curve in Fig. 2 and Fig. 3
Powder.
Embodiment 5
What is prepared concretely comprises the following steps：
Step 1, is first 0.82 according to the volume ratio of butyl titanate, second alcohol and water:13:8 ratio, by butyl titanate and second
After alcohol stirring mixing, water is added dropwise over thereto and the ethanol aqueous suspension for forming butyl titanate is stirred；Wherein, water is deionization
Water (or distilled water).Weight ratio according still further to calcium nitrate tetrahydrate, europium nitrate (III) hexahydrate and ethanol is 0.54：
0.052：14 ratio mixes three, obtains mixed solution.
Step 2, is first 0.6 according to the weight ratio of alkali, second alcohol and water：10.2：1 ratio mixes three；Wherein, water is
Deionized water (or distilled water), alkali is NaOH (or potassium hydroxide), obtains the ethanol water of alkali.According still further to butyl titanate
Ethanol aqueous suspension, mixed solution and alkali ethanol water volume ratio be 1.4：0.8：1.2 ratio, successively will mixing
After solution is added dropwise in the ethanol aqueous suspension of butyl titanate, 3.5h is stirred, obtain middle suspension, the ethanol of alkali is water-soluble
After liquid is added dropwise in middle suspension, 4h is stirred, obtain forerunner's white suspension.
Step 3, confined reaction 6h at forerunner's white suspension first is placed in into 220 DEG C, obtains reaction solution.Again to cooling after
Reaction solution carries out separation of solid and liquid, washing and dry treatment successively；Wherein, separation of solid and liquid is processed as centrifugation, and its rotating speed is
8000r/min, time are 2min, and carrying out washing treatment is isolated solid to be carried out 5 times using ethanol and deionized water
Alternately clean, it is centrifugation that solid is separated during cleaning, and dried process is that the solid after cleaning is placed at 70 DEG C to dry 5h.
It is obtained and is similar to shown in Fig. 1, and the europium-doped calcium titanate nano square fluorescent material as shown in the curve in Fig. 2 and Fig. 3.
Obviously, those skilled in the art can be to europium-doped calcium titanate nano square fluorescent material of the invention and its preparation
Method carries out various changes and modification without departing from the spirit and scope of the present invention.So, if to these modifications of the invention
Belong within the scope of the claims in the present invention and its equivalent technologies with modification, then the present invention is also intended to comprising these changes and becomes
Including type.
Claims (7)
1. a kind of europium-doped calcium titanate nano square fluorescent material, is made up of europium-doped calcium titanate nano particle, it is characterised in that：
The europium-doped calcium titanate nano particle is square block, the square length of side of the square block europium-doped calcium titanate for 245~
815nm。
2. a kind of preparation method of europium-doped calcium titanate nano square fluorescent material described in claim 1, including solvent-thermal method, it is special
It is key step as follows to levy：
Step 1, is first 0.62~0.82 according to the volume ratio of butyl titanate, second alcohol and water:13~17:1~8 ratio, by titanium
After acid butyl ester and ethanol stirring mixing, water is added dropwise over thereto and the ethanol aqueous suspension for forming butyl titanate is stirred, then pressed
Weight ratio according to calcium nitrate tetrahydrate, europium nitrate (III) hexahydrate and ethanol is 0.34~0.54：0.052~0.072：
10~14 ratio mixes three, obtains mixed solution；
Step 2, is first 0.4~0.6 according to the weight ratio of alkali, second alcohol and water：10.2~12.2：1 ratio mixes three, obtains
To the ethanol water of alkali, according still further to the volume of the ethanol water of the ethanol aqueous suspension, mixed solution and alkali of butyl titanate
Than being 1~1.4：0.8~1.2：0.8~1.2 ratio, the ethanol water that mixed solution is added dropwise over into butyl titanate successively is suspended
After in liquid, at least 1.5h is stirred, obtain middle suspension, after the ethanol water of alkali is added dropwise in middle suspension, stirred
At least 2h is mixed, forerunner's white suspension is obtained；
Step 3, confined reaction at least 6h at forerunner's white suspension first is placed in into 180~220 DEG C, obtains reaction solution, then to cold
But the reaction solution after carries out separation of solid and liquid, washing and dry treatment successively, and europium-doped calcium titanate nano square fluorescent material is obtained.
3. the preparation method of europium-doped calcium titanate nano square fluorescent material according to claim 2, it is characterized in that water is to go
Ionized water, or distilled water.
4. the preparation method of europium-doped calcium titanate nano square fluorescent material according to claim 2, it is characterized in that alkali is hydrogen
Sodium oxide molybdena, or potassium hydroxide.
5. the preparation method of europium-doped calcium titanate nano square fluorescent material according to claim 2, it is characterized in that solid-liquid point
From centrifugation is processed as, its rotating speed is 5000~8000r/min, the time is 2~6min.
6. the preparation method of europium-doped calcium titanate nano square fluorescent material according to claim 2, it is characterized in that washup
Reason is that the alternating that 3~5 times are carried out to isolated solid using ethanol and deionized water is cleaned, and solid is separated during cleaning
It is centrifugation.
7. the preparation method of europium-doped calcium titanate nano square fluorescent material according to claim 2, it is characterized in that at drying
Reason is 5~7h of baking at the solid after cleaning is placed in into 50~70 DEG C.
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