CN106701072B - Europium-doped calcium titanate nano square fluorescent powder and preparation method thereof - Google Patents
Europium-doped calcium titanate nano square fluorescent powder and preparation method thereof Download PDFInfo
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- CN106701072B CN106701072B CN201611196223.5A CN201611196223A CN106701072B CN 106701072 B CN106701072 B CN 106701072B CN 201611196223 A CN201611196223 A CN 201611196223A CN 106701072 B CN106701072 B CN 106701072B
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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 38
- 239000000843 powder Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 104
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 70
- 235000019441 ethanol Nutrition 0.000 claims abstract description 63
- 239000003513 alkali Substances 0.000 claims abstract description 39
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000926 separation method Methods 0.000 claims abstract description 34
- 239000000725 suspension Substances 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims abstract description 22
- 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
- 239000000243 solution Substances 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 21
- 238000004140 cleaning Methods 0.000 claims description 20
- 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 5
- 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
- 239000000463 material Substances 0.000 abstract description 8
- 238000001816 cooling Methods 0.000 abstract description 7
- 238000005406 washing Methods 0.000 abstract description 7
- 239000011575 calcium Substances 0.000 abstract description 6
- 238000004020 luminiscence type Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052791 calcium Inorganic materials 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000002242 deionisation method Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000010129 solution processing 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
- 229910052693 Europium Inorganic materials 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
- 230000005284 excitation Effects 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
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000002105 nanoparticle Substances 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
- 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 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
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect 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
- 239000000203 mixture Substances 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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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 a kind of europium-doped calcium titanate nano square fluorescent powders and preparation method thereof.Square fluorescent powder is that its side length is the square europium-doped calcium titanates of 245~815nm；Preparation method is first by butyl titanate, second alcohol and water is mixed to form the ethyl alcohol aqueous suspension of butyl titanate, again by calcium nitrate tetrahydrate, europium nitrate (III) hexahydrate and ethyl alcohol mixing, obtain mixed solution, later, first by alkali, the mixing of second alcohol and water, obtain the ethanol water of alkali, stirring after again successively instilling mixed solution in the ethyl alcohol aqueous suspension of butyl titanate, obtain intermediate suspension, stirring after the ethanol water of alkali is instilled in intermediate suspension, obtain forerunner's white suspension, finally, forerunner's white suspension is first placed in confined reaction at 180~220 DEG C, reaction solution after cooling is separated by solid-liquid separation again, washing and dry processing, purpose product is made.Its stimulated luminescence performance has obtained effective promotion, is extremely easy to widely be commercialized the fluorescent material as white light LEDs.
Description
Technical field
The present invention relates to a kind of square fluorescent powder and preparation method, especially a kind of europium-doped calcium titanate nano square fluorescence
Powder and preparation method thereof.
Background technique
White light LEDs are known as the green illumination light source of a new generation, have many relative to traditional incandescent lamp, fluorescent lamp etc.
Advantage, such as calorific value is small, energy saving, luminous efficiency is high, the service life is long, small in size, environmentally friendly.In addition to applying in lighting area,
White light LEDs application field further includes LCD backlight --- automobile, sound equipment instrument, cell phone back tabula rasa etc. and traffic lights, mark
Will lamp, information display screen etc..The major way that white light LEDs are realized combines first is that passing through single LED chip with fluorescent material
After issue white light, fluorescent material section or after all absorbing the light of the short wavelength that LED is issued issues visible light, last compound
Form white light.Calcium titanate with excellent optics, electricity, calorifics and mechanical performance, physical and chemical performance at normal temperature are non-
Often stablize；When as host material, after rare earth ion is mixed Ga acquisition fluorescent powders, with very high energy transmission
Efficiency is a kind of fluorescent material that potentially can be used for white light LEDs.People have made some to have to obtain this fluorescent material
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+
The structure and luminescent properties of emitting red light nano-phosphor are studied ", " 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, chemical general formula Ca1-xTiO3:xEu(0.01
≤ x≤0.10), pattern be that size is distributed in the irregular graininess of 70~170nm, most preferably excitation peak position in 397nm, most
Good transmitting peak position is 619nm；Preparation method is that isopropyl titanate, calcium carbonate, acetic acid, water and acetic acid europium are first passed through 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 be excited issue feux rouges, be used to combined with the light that LED chip issues after sending white light fluorescent material, but with its preparation side
All there is shortcomings for method, firstly, the purity of product is not high, the presence of the miscellaneous phase containing carbonate, miscellaneous phase generally be will affect
Transmitting of the energy in parent lattice is to there is more significant inhibiting effect to its fluorescence property；Secondly, size is unevenly distributed
The defect on one granular disintegration surface is more, and the perfection of lattice of product is bad, can also generate to its luminous efficiency certain
It influences；Again, preparation method also has the temperature of heat treatment excessively high in addition to it cannot obtain purity is high, the complete product of lattice
And lead to the defect of energy consumption.
Summary of the invention
The technical problem to be solved in the present invention in order to overcome the shortcomings in the prior art place, provide it is a kind of purity is high, lattice
Complete europium-doped calcium titanate nano square fluorescent powder.
The invention solves another technical problem be a kind of above-mentioned europium-doped calcium titanate nano square fluorescent powder is provided
Preparation method.
To solve technical problem of the invention, used technical solution are as follows: europium-doped calcium titanate nano square fluorescent powder
It is made of europium-doped calcium titanate nano particle, in particular,
The europium-doped calcium titanate nano particle is square, and the square side length of the square europium-doped calcium titanate is
245~815nm.
To solve another technical problem of the invention, another used technical solution are as follows: above-mentioned europium doped titanic acid
The preparation method of calcium nano square fluorescent powder includes solvent-thermal method, and especially key step is as follows:
Step 1, the first volume ratio according to butyl titanate (C16H36O4Ti), second alcohol and water is 0.62~0.82:13~17:
1~8 ratio after being stirred butyl titanate and ethyl alcohol, water is added dropwise thereto and stirs the second for forming butyl titanate
Alcohol aqueous suspension, according still further to calcium nitrate tetrahydrate (Ca (NO3)2·4H2O), europium nitrate (III) hexahydrate (Eu (NO3)3·
6H2O) and the weight ratio of ethyl alcohol is that 0.34~0.54:0.052~0.072:10~14 ratio mixes three, is mixed
Solution；
Step 2, first three is mixed for 0.4~0.6:10.2~12.2:1 ratio according to the weight ratio of alkali, second alcohol and water
It closes, obtains the ethanol water of alkali, according still further to the ethanol water of the ethyl alcohol aqueous suspension of butyl titanate, mixed solution and alkali
Volume ratio is 1~1.4:0.8~1.2:0.8~1.2 ratio, and mixed solution is successively added dropwise to the ethanol water of butyl titanate
After in suspension, at least 1.5h is stirred, intermediate suspension is obtained, the ethanol water of alkali is added dropwise in intermediate suspension
Afterwards, at least 2h is stirred, forerunner's white suspension is obtained；
Step 3, forerunner's white suspension is first placed in confined reaction at least 6h at 180~220 DEG C, obtains reaction solution, then
To the processing that reaction solution after cooling is successively separated by solid-liquid separation, is washed and is dried, it is glimmering that europium-doped calcium titanate nano square is made
Light powder.
The further improvement of preparation method as europium-doped calcium titanate nano square fluorescent powder:
Preferably, water is deionized water or distilled water.
Preferably, alkali is sodium hydroxide or potassium hydroxide.
Preferably, solid-liquid separation treatment is centrifuge separation, and revolving speed is 5000~8000r/min, the time is 2~6min.
Preferably, carrying out washing treatment is the alternating for carrying out 3~5 times to isolated solid using ethyl alcohol and deionized water
Cleaning, separation solid is centrifuge separation when cleaning.
Preferably, it is dried as the solid after cleaning is placed in 5~7h of baking at 50~70 DEG C.
Beneficial effect compared with the existing technology is:
First, using scanning electron microscope, X-ray diffractometer and Fluorescence Spectrometer carry out table respectively to purpose product obtained
Sign, as a result, it can be seen that, the pattern of purpose product is square, and the side length of square is 245~815nm；Ingredient is europium doping
Calcium titanate, chemical general formula Ca1-xTiO3:xEu(0.01≤x≤0.11)；Best excitation peak is located at 395nm, best emission peak
Positioned at 615nm.This purpose product being made of square europium-doped calcium titanate, both since europium-doped calcium titanate is square,
And make it not only good crystallinity, surface are smooth, and lattice defect is few, pole is conducive to the enhancing of fluorescence intensity, while also having dispersion
Good, the not easy to reunite advantage of property；Again because of the excited fluorescence speciality of europium-doped calcium titanate itself；Due also in europium-doped calcium titanate not
Containing miscellaneous phase；To make the stimulated luminescence performance of purpose product obtain effective promotion.
Second, preparation method is scientific, efficient.Purity is high, the complete purpose product of lattice has not only been made --- europium doping
Calcium titanate nano square fluorescent powder；Also make it have higher stimulated luminescence performance；The purpose product more having is only
The europium-doped calcium titanate of pure phase, and the temperature of reaction are low --- energy conservation, thus the characteristics of being easy to industrial-scale production；In turn
Purpose product is set to be extremely easy to widely be commercialized the fluorescent material as white light LEDs.
Detailed description of the invention
Fig. 1 is one of the result for using scanning electron microscope (SEM) to be characterized purpose product made from preparation method.SEM
Image shows purpose product for the good square of dispersibility.
Fig. 2 is one of the result for using X-ray diffraction (XRD) instrument to be characterized purpose product obtained.Wherein, XRD
The bottom curve of spectrogram is the XRD standard spectral line of orthorhombic phase calcium titanate, the spectral line that upper curve is purpose product；The XRD spectra
Show that purpose product is orthorhombic phase calcium titanate, without impurity phase, and the doping of rare earth ion generates significantly crystal phase
It influences.
Fig. 3 is one of the result characterized to purpose product obtained using steady-state lifetime Fluorescence Spectrometer.Fluorescence light
Spectral line in spectrogram shows that the maximum excitation wavelength of purpose product is located at 395nm, best launch wavelength is located at 615nm, by
It is it is found that purpose product can efficiently be excited by purple light and issue feux rouges.In conjunction with Fig. 2 it is found that the ingredient of purpose product is changed for it
General formula is Ca1-xThe europium-doped calcium titanate of TiO3:xEu (0.01≤x≤0.11).
Specific embodiment
Preferred embodiment of the invention is described in further detail with reference to the accompanying drawing.
It buys from market or is voluntarily made first:
Butyl titanate；
Ethyl alcohol；
Deionized water and distilled water as water；
Calcium nitrate tetrahydrate；
Europium nitrate (III) hexahydrate；
Sodium hydroxide and potassium hydroxide as alkali.
Then,
Embodiment 1
The specific steps of preparation are as follows:
Step 1, the ratio for being first 0.62:17:1 according to the volume ratio of butyl titanate, second alcohol and water, by butyl titanate and second
After alcohol is stirred, water is added dropwise thereto and stirs the ethyl alcohol aqueous suspension for forming butyl titanate；Wherein, water is deionization
Water (or distilled water).Weight ratio according still further to calcium nitrate tetrahydrate, europium nitrate (III) hexahydrate and ethyl alcohol is 0.34:
The ratio of 0.072:10 mixes three, obtains mixed solution.
Step 2, first three is mixed according to the ratio that the weight ratio of alkali, second alcohol and water is 0.4:12.2:1；Wherein, water is
Deionized water (or distilled water), alkali are sodium hydroxide (or potassium hydroxide), obtain the ethanol water of alkali.According still further to butyl titanate
Ethyl alcohol aqueous suspension, mixed solution and alkali ethanol water volume ratio be 1:1.2:0.8 ratio, will successively mix molten
After liquid is added dropwise in the ethyl alcohol aqueous suspension of butyl titanate, 1.5h is stirred, intermediate suspension is obtained, by the ethanol water of alkali
After being added dropwise in intermediate suspension, 2h is stirred, forerunner's white suspension is obtained.
Step 3, forerunner's white suspension is first placed in confined reaction at 180 DEG C and for 24 hours, obtains reaction solution.Again to cooling after
The reaction solution processing that is successively separated by solid-liquid separation, is washed and is dried；Wherein, solid-liquid separation treatment is centrifuge separation, revolving speed
For 5000r/min, time 6min, carrying out washing treatment is to be carried out 3 times using ethyl alcohol and deionized water to isolated solid
Alternating cleaning, separation solid is centrifuge separation when cleaning, is dried as the solid after cleaning is placed at 50 DEG C and is dried
7h.It is made and is similar to shown in Fig. 1, and the europium-doped calcium titanate nano square fluorescent powder as shown in the curve in Fig. 2 and Fig. 3.
Embodiment 2
The specific steps of preparation are as follows:
Step 1, the ratio for being first 0.67:16:3 according to the volume ratio of butyl titanate, second alcohol and water, by butyl titanate and second
After alcohol is stirred, water is added dropwise thereto and stirs the ethyl alcohol aqueous suspension for forming butyl titanate；Wherein, water is deionization
Water (or distilled water).Weight ratio according still further to calcium nitrate tetrahydrate, europium nitrate (III) hexahydrate and ethyl alcohol is 0.39:
The ratio of 0.067:11 mixes three, obtains mixed solution.
Step 2, first three is mixed according to the ratio that the weight ratio of alkali, second alcohol and water is 0.45:11.7:1；Wherein, water
For deionized water (or distilled water), alkali is sodium hydroxide (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 ethyl alcohol aqueous suspension of ester, mixed solution and alkali is the ratio of 1.1:1.1:0.9, will successively be mixed
After conjunction solution is added dropwise in the ethyl alcohol aqueous suspension of butyl titanate, 2h is stirred, intermediate suspension is obtained, the ethyl alcohol of alkali is water-soluble
After liquid is added dropwise in intermediate suspension, 2.5h is stirred, forerunner's white suspension is obtained.
Step 3, forerunner's white suspension is first placed in confined reaction 20h at 190 DEG C, obtains reaction solution.Again to cooling after
The reaction solution processing that is successively separated by solid-liquid separation, is washed and is dried；Wherein, solid-liquid separation treatment is centrifuge separation, revolving speed
For 6000r/min, time 5min, carrying out washing treatment is to be carried out 3 times using ethyl alcohol and deionized water to isolated solid
Alternating cleaning, separation solid is centrifuge separation when cleaning, is dried as the solid after cleaning is placed at 55 DEG C and is dried
6.5h.It is made 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
The specific steps of preparation are as follows:
Step 1, the ratio for being first 0.72:15:5 according to the volume ratio of butyl titanate, second alcohol and water, by butyl titanate and second
After alcohol is stirred, water is added dropwise thereto and stirs the ethyl alcohol aqueous suspension for forming butyl titanate；Wherein, water is deionization
Water (or distilled water).Weight ratio according still further to calcium nitrate tetrahydrate, europium nitrate (III) hexahydrate and ethyl alcohol is 0.44:
The ratio of 0.062:12 mixes three, obtains mixed solution.
Step 2, first three is mixed according to the ratio that the weight ratio of alkali, second alcohol and water is 0.5:11.2:1；Wherein, water is
Deionized water (or distilled water), alkali are sodium hydroxide (or potassium hydroxide), obtain the ethanol water of alkali.According still further to butyl titanate
Ethyl alcohol 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 ethyl alcohol aqueous suspension of butyl titanate, stir 2.5h, obtain intermediate suspension, by the ethanol water of alkali by
After being added dropwise in intermediate suspension, 3h is stirred, forerunner's white suspension is obtained.
Step 3, forerunner's white suspension is first placed in confined reaction 15h at 200 DEG C, obtains reaction solution.Again to cooling after
The reaction solution processing that is successively separated by solid-liquid separation, is washed and is dried；Wherein, solid-liquid separation treatment is centrifuge separation, revolving speed
For 6500r/min, time 4min, carrying out washing treatment is to be carried out 4 times using ethyl alcohol and deionized water to isolated solid
Alternating cleaning, separation solid is centrifuge separation when cleaning, is dried as the solid after cleaning is placed at 60 DEG C and is dried
6h.It is made as shown in Figure 1, and the europium-doped calcium titanate nano square fluorescent powder as shown in the curve in Fig. 2 and Fig. 3.
Embodiment 4
The specific steps of preparation are as follows:
Step 1, the ratio for being first 0.77:14:7 according to the volume ratio of butyl titanate, second alcohol and water, by butyl titanate and second
After alcohol is stirred, water is added dropwise thereto and stirs the ethyl alcohol aqueous suspension for forming butyl titanate；Wherein, water is deionization
Water (or distilled water).Weight ratio according still further to calcium nitrate tetrahydrate, europium nitrate (III) hexahydrate and ethyl alcohol is 0.49:
The ratio of 0.057:13 mixes three, obtains mixed solution.
Step 2, first three is mixed according to the ratio that the weight ratio of alkali, second alcohol and water is 0.55:10.7:1；Wherein, water
For deionized water (or distilled water), alkali is sodium hydroxide (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 ethyl alcohol aqueous suspension of ester, mixed solution and alkali is the ratio of 1.3:0.9:1.1, will successively be mixed
After conjunction solution is added dropwise in the ethyl alcohol aqueous suspension of butyl titanate, 3h is stirred, intermediate suspension is obtained, the ethyl alcohol of alkali is water-soluble
After liquid is added dropwise in intermediate suspension, 3.5h is stirred, forerunner's white suspension is obtained.
Step 3, forerunner's white suspension is first placed in confined reaction 10h at 210 DEG C, obtains reaction solution.Again to cooling after
The reaction solution processing that is successively separated by solid-liquid separation, is washed and is dried；Wherein, solid-liquid separation treatment is centrifuge separation, revolving speed
For 7000r/min, time 3min, carrying out washing treatment is to be carried out 4 times using ethyl alcohol and deionized water to isolated solid
Alternating cleaning, separation solid is centrifuge separation when cleaning, is dried as the solid after cleaning is placed at 65 DEG C and is dried
5.5h.It is made 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
The specific steps of preparation are as follows:
Step 1, the ratio for being first 0.82:13:8 according to the volume ratio of butyl titanate, second alcohol and water, by butyl titanate and second
After alcohol is stirred, water is added dropwise thereto and stirs the ethyl alcohol aqueous suspension for forming butyl titanate；Wherein, water is deionization
Water (or distilled water).Weight ratio according still further to calcium nitrate tetrahydrate, europium nitrate (III) hexahydrate and ethyl alcohol is 0.54:
The ratio of 0.052:14 mixes three, obtains mixed solution.
Step 2, first three is mixed according to the ratio that the weight ratio of alkali, second alcohol and water is 0.6:10.2:1；Wherein, water is
Deionized water (or distilled water), alkali are sodium hydroxide (or potassium hydroxide), obtain the ethanol water of alkali.According still further to butyl titanate
Ethyl alcohol 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 ethyl alcohol aqueous suspension of butyl titanate, 3.5h is stirred, intermediate suspension is obtained, the ethyl alcohol of alkali is water-soluble
After liquid is added dropwise in intermediate suspension, 4h is stirred, forerunner's white suspension is obtained.
Step 3, forerunner's white suspension is first placed in confined reaction 6h at 220 DEG C, obtains reaction solution.Again to after cooling
The processing that reaction solution is successively separated by solid-liquid separation, is washed and is dried；Wherein, solid-liquid separation treatment is centrifuge separation, and revolving speed is
8000r/min, time 2min, carrying out washing treatment are to be carried out 5 times using ethyl alcohol and deionized water to isolated solid
It alternately cleans, separation solid is centrifuge separation when cleaning, is dried as the solid after cleaning is placed at 70 DEG C and dries 5h.
It is made and is similar to shown in Fig. 1, and the europium-doped calcium titanate nano square fluorescent powder 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 powder of the invention and its preparation
Method carries out various modification and variations without departing from the spirit and scope of the present invention.If in this way, to these modifications of the invention
Within the scope of the claims of the present invention and its equivalent technology with modification, then the present invention is also intended to encompass these changes and becomes
Including type.
Claims (6)
1. a kind of preparation method of europium-doped calcium titanate nano square fluorescent powder, including solvent-thermal method, it is characterised in that main step
It is rapid as follows:
Step 1, the first volume ratio according to butyl titanate, second alcohol and water is 0.62~0.82:13~17:1~8 ratio, by titanium
After acid butyl ester and ethyl alcohol are stirred, water is added dropwise thereto and stirs the ethyl alcohol aqueous suspension for forming butyl titanate, then presses
Weight ratio according to calcium nitrate tetrahydrate, europium nitrate (III) hexahydrate and ethyl alcohol is 0.34~0.54:0.052~0.072:
10~14 ratio mixes three, obtains mixed solution；
Step 2, first three is mixed for 0.4~0.6:10.2~12.2:1 ratio according to the weight ratio of alkali, second alcohol and water, is obtained
To the ethanol water of alkali, according still further to the volume of the ethanol water of the ethyl alcohol aqueous suspension of butyl titanate, mixed solution and alkali
Than for 1~1.4:0.8~1.2:0.8~1.2 ratio, the ethanol water that butyl titanate successively is added dropwise in mixed solution is suspended
After in liquid, at least 1.5h is stirred, intermediate suspension is obtained, after the ethanol water of alkali is added dropwise in intermediate suspension, stirs
At least 2h is mixed, forerunner's white suspension is obtained；
Step 3, forerunner's white suspension is first placed in confined reaction at least 6h at 180~220 DEG C, obtains reaction solution, then to cold
But europium-doped calcium titanate nano square fluorescent powder is made in the processing that the reaction solution after is successively separated by solid-liquid separation, is washed and is dried；
The side length of the nano square of the europium-doped calcium titanate nano square fluorescent powder is 245~815nm.
2. the preparation method of europium-doped calcium titanate nano square fluorescent powder according to claim 1, it is characterized in that water is to go
Ionized water or distilled water.
3. the preparation method of europium-doped calcium titanate nano square fluorescent powder according to claim 1, it is characterized in that alkali is hydrogen
Sodium oxide molybdena or potassium hydroxide.
4. the preparation method of europium-doped calcium titanate nano square fluorescent powder according to claim 1, it is characterized in that solid-liquid point
It is centrifuge separation from processing, revolving speed is 5000~8000r/min, the time is 2~6min.
5. the preparation method of europium-doped calcium titanate nano square fluorescent powder according to claim 1, it is characterized in that washup
Reason is cleaned for the alternating for carrying out 3~5 times to isolated solid using ethyl alcohol and deionized water, and when cleaning separates solid
For centrifuge separation.
6. the preparation method of europium-doped calcium titanate nano square fluorescent powder according to claim 1, it is characterized in that at dry
Reason dries 5~7h for the solid after cleaning to be placed at 50~70 DEG C.
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