CN107841306A - A kind of divalent europium activation glassy state fluorescent material and its preparation method and application - Google Patents
A kind of divalent europium activation glassy state fluorescent material and its preparation method and application Download PDFInfo
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- CN107841306A CN107841306A CN201710999893.9A CN201710999893A CN107841306A CN 107841306 A CN107841306 A CN 107841306A CN 201710999893 A CN201710999893 A CN 201710999893A CN 107841306 A CN107841306 A CN 107841306A
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- 239000000463 material Substances 0.000 title claims abstract description 70
- 229910052693 Europium Inorganic materials 0.000 title claims abstract description 18
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 230000004913 activation Effects 0.000 title claims description 11
- 239000010457 zeolite Substances 0.000 claims abstract description 27
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 26
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000012298 atmosphere Substances 0.000 claims abstract description 15
- 150000002500 ions Chemical class 0.000 claims abstract description 12
- 229910001388 sodium aluminate Inorganic materials 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 238000006862 quantum yield reaction Methods 0.000 claims abstract description 6
- 238000005341 cation exchange Methods 0.000 claims abstract description 3
- 230000005284 excitation Effects 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 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 4
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- WLYAEQLCCOGBPV-UHFFFAOYSA-N europium;sulfuric acid Chemical compound [Eu].OS(O)(=O)=O WLYAEQLCCOGBPV-UHFFFAOYSA-N 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 238000010791 quenching Methods 0.000 abstract description 3
- 230000000171 quenching effect Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 10
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical class O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910003564 SiAlON Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910016644 EuCl3 Inorganic materials 0.000 description 1
- 150000000918 Europium Chemical class 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- GEIGXJHXQWKQAT-UHFFFAOYSA-N europium;nitric acid Chemical compound [Eu].O[N+]([O-])=O GEIGXJHXQWKQAT-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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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- 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 provides a kind of divalent europium to activate glassy state fluorescent material, chemical general formula xEu2+·(1‑x)Na2O·Al2O3·nSiO2, wherein x span is 0<X≤1, n span are 12≤n≤54.The fluorescent material of the present invention uses USY zeolite Na2O·Al2O3·nSiO2For raw material, by Eu3+Cation exchange is carried out in deionized water solution, and is heat-treated and obtains in reducing atmosphere.Eu in the fluorescent material of the present invention2+Ion distribution is uniform, and the blue emission in the case where 200~420nm ultraviolet light broadbands excite has higher fluorescence quantum yield, and with very excellent resisting temperature quenching characteristic and good physical and chemical stability.Preparation method of the invention is simple, cost is cheap, nontoxic, pollution-free, suitable for large-scale industrial production.
Description
Technical field
The invention belongs to fluorescent material technical field, more particularly to a kind of divalent europium activation glassy state fluorescent material and
Its preparation method.
Background technology
White light emitting diode (LED) has low energy consumption, efficiency high, long lifespan etc. excellent as a kind of solid light source
Point, it is considered to be the forth generation new light sources after incandescent lamp, fluorescent lamp, high-intensity discharge (HID) lamp.At present, it is commercial white
Light LED mainly excites Ce using GaInN base blue-light LED chips3+:YAG yellow fluorescent powders.But this light source is red due to lacking
Light composition and there is the higher (CCT of colour temperature>6500K), the problems such as colour rendering index relatively low (CRI~70), indoor photograph is not suitable for it
The fields such as bright and display.
Solving the above problems has two methods：(1) fluorescent material of feux rouges is launched in addition on the basis of blue-light LED chip；(2)
Three primary colours (RGB) phosphor emission white light is excited using near ultraviolet LED chip.Wherein, the latter is relative to the advantages of the former,
Fluorescent material can all absorb ultraviolet light under proper condition, avoid it from reaching human eye, so as to eliminate high-energy photon to human eye
Cause to damage.In addition, near ultraviolet excitation fluorescent material also has important application in fields such as antifraud marker, toy, decorations.
In the prior art, the phosphor for producing other longer wavelengths of visible rays is excited using the royal purple or blue light of near ultraviolet
Material is typically from europkium-activated nitrogen oxides, nitride, oxide or sulfide etc..For example, Chinese invention patent
200610058559.5 disclose a kind of luminescent device, and it is predominantly europkium-activated using royal purple or blue light activated fluorescent material
Nitrogen oxides and nitride, wherein produce green or green-yellow light fluorescent material activates β-SiAlON for europium, produce yellowish green, yellow or yellow
The fluorescent material of feux rouges is that europium activates α-SiAlON, and it is crystal of nitride red fluorescence material to produce yellow red or feux rouges fluorescent material
Expect (Ca, Eu) AlSiN3.However, relative to nitrogen oxides or nitride fluorescent material, oxide and all-sulphide phosphor
Physical and chemical stability, such as durability and high-temperature behavior, compare shortcoming.
In addition, activation ion can usually produce Cluster Phenomenon in the carrier in the prior art, can not be evenly distributed,
So as to have impact on its fluorescence quantum efficiency, and its preparation method is typically more complicated, raw material generally has certain toxicity or
Pollute larger.
The content of the invention
In view of the drawbacks described above of prior art, it is an object of the invention to provide a kind of divalent europium to activate glassy state
Fluorescent material, it is derived from ultrastable (USY zeolite), the blue light hair in the case where 200~420nm ultraviolet light broadbands excite
Penetrating has higher fluorescence quantum yield, and stable with very excellent resisting temperature quenching characteristic and good physical chemistry
Property.Meanwhile the controllability and uniformity of its preparation method are high, cost is cheap, nontoxic, pollution-free.It is in addition, provided by the invention glimmering
Luminescent material has important application in height colour developing, high-brightness LED, and anti-counterfeit field.
According to the first aspect of the invention, the invention provides a kind of divalent europium to activate glassy state fluorescent material,
Its chemical general formula is xEu2+·(1-x)Na2O·Al2O3·nSiO2, wherein x span is 0<X≤1, n span
It is 12≤n≤54.
The fluorescent material of the present invention launches blue light under 200~420nm ultraviolet excitations, and it has higher fluorescent quantum
Yield, typically 50%~98%.
According to the second aspect of the invention of the present invention, present invention also offers above-mentioned divalent europium to activate glassy state
The preparation method of fluorescent material.The fluorescent material of the present invention uses USY zeolite Na2O·Al2O3·nSiO2(12≤n≤54, inhale
Attached water does not mark) it is raw material, in Eu3+Ion exchange is carried out in deionized water solution；After ion exchange, Eu is contained in duct3+Ion
Zeolite slurry it is cleaned, drying after, be heat-treated in reducing atmosphere, single-phase glassy state thing phase generated by phase transformation；Meanwhile
In the presence of reducing atmosphere, make Eu3+Ion transit is Eu2+, so as to obtain Eu2+The ion-activated glass derived from USY zeolite
Glass state fluorescent material.The preparation method of the present invention specifically includes following steps：
(1) by USY zeolite Na2O·Al2O3·nSiO2With Eu3+Deionized water solution carries out cation exchange, obtains in duct
Contain Eu3+The zeolite slurry of ion；
(2) the zeolite slurry for obtaining step (1) passes through separation of solid and liquid, and the solid obtained after separation of solid and liquid is cleaned,
Dry, obtain zeolite powder；
(3) zeolite powder that step (2) obtains is placed in reducing atmosphere and be heat-treated, phosphor is obtained after cooling
Expect xEu2+·(1-x)Na2O·Al2O3·nSiO2。
Preferably, the USY zeolite Na in step (1)2O·Al2O3·nSiO2Silica alumina ratio be 6~27:1, i.e., 12
≤n≤54。
Preferably, the Eu in step (1)3+The solute of deionized water solution is selected from the water solubilitys such as europium nitrate, Europium chloride, europium sulfate
One or more in trivalent europium salt.
Preferably, the separation of solid and liquid in step (2) is by centrifuging or filtering.
Preferably, the reducing atmosphere in step (3) is nitrogen atmosphere, hydrogen nitrogen mixed gas atmosphere or carbon monoxide atmosphere, atmosphere
Pressure can be normal pressure, negative pressure or malleation.
Preferably, the temperature of the heat treatment of step (3) is 600~1300 DEG C, more preferably 800~1100 DEG C；Heat treatment
Time be 0.5~72 hour, more preferably 2~48 hours.
According to the third aspect of the present invention, divalent europium of the invention activation glassy state fluorescent material can be used as LED
Fluorescent material and anti-fake material application, be particularly applied to high colour developing, the LED of high brightness.
Compared with prior art, divalent europium activation glassy state fluorescent material Eu provided by the present invention2+Ion distribution
Uniformly, the blue emission in the case where 200~420nm ultraviolet light broadbands excite has higher fluorescence quantum yield, and with non-
Chang Youyi resisting temperature quenching characteristic and good physical and chemical stability.Divalent europium provided by the present invention activates glass
The preparation method of state fluorescent material is simple, and cost is cheap, nontoxic, pollution-free to be applied to large-scale industrial production.
Brief description of the drawings
Fig. 1 is the X ray diffracting spectrum for the fluorescent material that the embodiment of the present invention 1 is prepared；
Fig. 2 is the fluorescence spectrum of fluorescent material that the embodiment of the present invention 1 is prepared under 365nm ultraviolet excitations；
Fig. 3 is the X ray diffracting spectrum for the fluorescent material that the embodiment of the present invention 2 is prepared；
Fig. 4 is the fluorescence spectrum of fluorescent material that the embodiment of the present invention 2 is prepared under 365nm ultraviolet excitations.
Embodiment
Embodiments of the invention are elaborated below, following embodiments is under premised on technical solution of the present invention
Implemented, give detailed embodiment and specific operating process, but protection scope of the present invention be not limited to it is following
Embodiment.
Embodiment 1
The fluorescent material that embodiment 1 prepares the present invention comprises the following steps：
(1) with USY zeolite Na2O·Al2O3·nSiO2(n=12, i.e. silica alumina ratio are 6:And europium nitrate Eu (NO 1)3)3·
6H2O is raw material, by Eu in theory3+All substitution Na+Ion calculates, and weighs USY zeolite and europium nitrate.By USY zeolite and nitric acid
Europium, which is put into beaker, adds deionized water, is placed on agitator and continuously stirs more than 24h to carry out ion exchange, obtains in duct
Contain Eu3+The zeolite slurry of ion.
(2) the zeolite slurry for obtaining step (1) is centrifuged or filtered, cleaned successively, is put into electric drying chamber drying
The 6h zeolite powders derived above by ion exchange.
(3) powder that step (2) obtains is put into high temperature process furnances it is passed through hydrogen-nitrogen mixture gas at a high temperature of 950 DEG C and locates
3h is managed, is taken out after sample is down to room temperature and obtains a kind of glassy state fluorescent material.
The thing phase of the fluorescent material obtained using X-ray diffractometer (XRD) testing example 1, test result such as Fig. 1 institutes
Show, test result shows that the fluorescent material that the embodiment of the present invention 1 obtains is glassy state.
It is luminous under 365nm ultraviolet excitations using the fluorescent material that XRF testing example 1 is prepared
Spectrum, test result are as shown in Figure 2.As shown in Figure 2, the fluorescent material that embodiment 1 is prepared can under the exciting of ultraviolet light
Blue light is produced, the luminous peak position of blue light is in 455nm or so, luminous peak width≤76nm.Using integrating sphere combination fluorescence spectrum
Instrument, it is about 80% to measure fluorescence quantum yield of the material under 365nm ultraviolet excitations.
Embodiment 2
The method that embodiment 2 prepares fluorescent material is substantially the same manner as Example 1, only difference is that in step (3) at heat
The temperature of reason is 1000 DEG C.
The same fluorescent material that embodiment 2 is prepared using X-ray diffractometer and XRF is detected, and is examined
Survey result difference as shown in Figure 3,4.Wherein, Fig. 3 shows that the fluorescent material that embodiment 2 obtains still is glassy state.Fig. 4 shows
It is 445.6nm blue lights that peak wavelength can be sent under 365nm ultraviolet excitations.
Embodiment 3
The method that embodiment 3 prepares fluorescent material is substantially the same manner as Example 1, only difference is that in step (3) at heat
The time of reason is 2h.
The same fluorescent material that embodiment 3 is prepared using X-ray diffractometer and XRF is detected, and is examined
Survey result and show that gained fluorescent material is still glassy state, blue light can be equally sent under 365nm ultraviolet excitations.
Embodiment 4
The method that embodiment 4 prepares fluorescent material is substantially the same manner as Example 1, only difference is that in step (3) at heat
The atmosphere of reason is hydrogen atmosphere.
The same fluorescent material that embodiment 4 is prepared using X-ray diffractometer and XRF is detected, and is examined
Survey result and show that gained fluorescent material is still glassy state, blue light can be equally sent under 365nm ultraviolet excitations.
Embodiment 5
The method that embodiment 5 prepares fluorescent material is substantially the same manner as Example 1, only difference is that in step (1) and selects
The silica alumina ratio of USY zeolite be 22:1 (i.e. n=44).
The same fluorescent material that embodiment 4 is prepared using X-ray diffractometer and XRF is detected, and is examined
Survey result and show that gained fluorescent material is still glassy state, blue light can be equally sent under 365nm ultraviolet excitations.
Embodiment 6
The method that embodiment 6 prepares fluorescent material is substantially the same manner as Example 1, only difference is that in step (1) and selects
The silica alumina ratio of USY zeolite be 27:1 (i.e. n=54).
The same fluorescent material that embodiment 4 is prepared using X-ray diffractometer and XRF is detected, and is examined
Survey result and show that gained fluorescent material is still glassy state, blue light can be equally sent under 365nm ultraviolet excitations.
Embodiment 7
The method that embodiment 7 prepares fluorescent material is substantially the same manner as Example 1, only difference is that in step (1) and selects
Europium chloride EuCl3As Eu3+Ion raw material.
The same fluorescent material that embodiment 4 is prepared using X-ray diffractometer and XRF is detected, and is examined
Survey result and show that gained fluorescent material is still glassy state, blue light can be equally sent under 365nm ultraviolet excitations.
From above example, the invention provides a kind of divalent europium derived from USY zeolite to activate glassy state
The preparation method of fluorescent material, because zeolite materials are the conventional raw materials of petroleum industry catalyst, cheap, great cost is excellent
Gesture.Meanwhile USY zeolite has a highly stable physical and chemical performance as the crystalline material with cycle loose structure, and have from
Sub- exchange capacity, therefore activation ion can be evenly distributed in its duct by aqueous solution ion-exchange method, then lead to
Cross reducing atmosphere be heat-treated so that can obtain activation ion distribution uniformly, uniformity is very good, physical and chemical performance is stable
Fluorescent material.
Preferred embodiment of the invention described in detail above.It should be appreciated that the ordinary skill of this area is without wound
The property made work can makes many modifications and variations according to the design of the present invention.Therefore, all technician in the art
Pass through logic analysis, reasoning or the available technology of limited experiment on the basis of existing technology under this invention's idea
Scheme, all should be in the protection domain being defined in the patent claims.
Claims (10)
1. a kind of divalent europium activates glassy state fluorescent material, it is characterised in that the chemical general formula of the fluorescent material is xEu2 +·(1-x)Na2O·Al2O3·nSiO2, wherein x span is 0<X≤1, n span are 12≤n≤54.
2. divalent europium as claimed in claim 1 activates glassy state fluorescent material, it is characterised in that the fluorescent material exists
Launch blue light under 200~420nm ultraviolet excitations, its fluorescence quantum yield is 50%~98%.
3. the preparation method of divalent europium activation glassy state fluorescent material as claimed in claim 1, it is characterised in that described
Preparation method comprises the following steps：
(1) by USY zeolite Na2O·Al2O3·nSiO2With Eu3+Deionized water solution carries out cation exchange, obtains containing in duct
Eu3+The zeolite slurry of ion；
(2) the zeolite slurry for obtaining step (1) passes through separation of solid and liquid, and the solid obtained after the separation of solid and liquid is clear
Wash, dry, obtain zeolite powder；
(3) zeolite powder that step (2) obtains is placed in reducing atmosphere and be heat-treated, obtained after cooling described glimmering
Luminescent material xEu2+·(1-x)Na2O·Al2O3·nSiO2。
4. preparation method as claimed in claim 3, it is characterised in that Eu described in step (1)3+The solute choosing of deionized water solution
One or more from europium nitrate, Europium chloride, europium sulfate.
5. preparation method as claimed in claim 3, it is characterised in that separation of solid and liquid described in step (2) be by centrifugation or
Filter.
6. preparation method as claimed in claim 3, it is characterised in that reducing atmosphere described in step (3) is nitrogen atmosphere, hydrogen
Nitrogen mixed gas atmosphere or carbon monoxide atmosphere.
7. preparation method as claimed in claim 3, it is characterised in that the temperature being heat-treated described in step (3) be 600~
1300 DEG C, the time of the heat treatment is 0.5~72 hour.
8. preparation method as claimed in claim 7, it is characterised in that the temperature of the heat treatment is 800~1100 DEG C, described
The time of heat treatment is 2~48 hours.
9. application of the divalent europium activation glassy state fluorescent material as claimed in claim 1 as LED fluorescent materials.
10. application of the divalent europium activation glassy state fluorescent material as claimed in claim 1 as anti-fake material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108893109A (en) * | 2018-08-31 | 2018-11-27 | 上海理工大学 | A kind of divalent europium activates the preparation method of six side's nepheline phase fluorescent materials |
| CN113716871A (en) * | 2021-09-08 | 2021-11-30 | 深圳爱尔创口腔技术有限公司 | Fluorescent lithium silicate glass ceramic enhanced by ion exchange and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007005795A1 (en) * | 2005-07-01 | 2007-01-11 | Albemarle Netherlands Bv | Use of anionic clay in an fcc process |
| CN101445728A (en) * | 2008-12-26 | 2009-06-03 | 上海师范大学 | Blue fluorescent material excited by broadband ultraviolet and preparation method thereof |
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2017
- 2017-10-24 CN CN201710999893.9A patent/CN107841306A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007005795A1 (en) * | 2005-07-01 | 2007-01-11 | Albemarle Netherlands Bv | Use of anionic clay in an fcc process |
| CN101445728A (en) * | 2008-12-26 | 2009-06-03 | 上海师范大学 | Blue fluorescent material excited by broadband ultraviolet and preparation method thereof |
Non-Patent Citations (9)
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108893109A (en) * | 2018-08-31 | 2018-11-27 | 上海理工大学 | A kind of divalent europium activates the preparation method of six side's nepheline phase fluorescent materials |
| CN108893109B (en) * | 2018-08-31 | 2021-04-30 | 上海理工大学 | Preparation method of divalent europium ion activated cancrinite phase fluorescent material |
| CN113716871A (en) * | 2021-09-08 | 2021-11-30 | 深圳爱尔创口腔技术有限公司 | Fluorescent lithium silicate glass ceramic enhanced by ion exchange and preparation method thereof |
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