CN106010530A - Green long-afterglow luminescent material and preparation method thereof - Google Patents
Green long-afterglow luminescent material and preparation method thereof Download PDFInfo
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- CN106010530A CN106010530A CN201610553144.9A CN201610553144A CN106010530A CN 106010530 A CN106010530 A CN 106010530A CN 201610553144 A CN201610553144 A CN 201610553144A CN 106010530 A CN106010530 A CN 106010530A
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Abstract
The invention discloses a green long-afterglow luminescent material and a preparation method of the green long-afterglow luminescent material, and relates to the long-afterglow luminescent material. The general formula of the chemical composition of the green long-afterglow luminescent material is aCaO.bSc2O3.cCeO2, wherein a is more than or equal to 0.5 and less than or equal to 1, b is more than or equal to 0.8 and less than or equal to 1.2, and c is more than or equal to 0.001 and less than or equal to 0.1. The preparation method of the green long-afterglow luminescent material comprises the following steps of: weighing and grinding oxides or corresponding salts of components according to the molar ratio of a, b and c; performing presintering, reducing the temperature to the room temperature, and performing grinding and mixing again; performing sintering in reducing atmosphere, and performing crushing after cooling, thus obtaining the green long-afterglow luminescent material. The green long-afterglow luminescent material takes Ca (Calcium), Sc (Scandium) and O (Oxygen) as basic matrix elements, and Ce<3+> as an afterglow luminescence center, and the own trap number of a matrix material is increased to adjust the luminous intensity of long afterglow. According to the invention, the synthesis is simple and the afterglow intensity is high; furthermore, other energy storage defect centers are not required to be introduced; after ultraviolet-visible light irradiation, the strong green long-afterglow luminescence can be visible to naked eyes.
Description
Technical field
The present invention relates to long after glow luminous material, especially relate to Ce3+Ion is a kind of green long afterglow at afterglow center
Luminescent material and preparation method thereof.
Background technology
Long-afterglow material can absorb the energy of extraneous radiation and be stored, and remains to continue luminescence after stopping irradiation, because of
This is widely used in the fields such as Emergency Light and display, aviation, automobile instrument display panel.For the system of long-afterglow material,
The most traditional long-afterglow material is concentrated mainly on ZnS, CaS sulfides system, this system existence and stability difference easily decomposition,
The deficiencies such as hygroscopicity is strong, afterglow performance is weak.Aluminates system is widely studied and develops subsequently, wherein SrAl2O4:Eu2+,
Dy3+Green glow long-afterglow material becomes main commercial long-afterglow material, has stable chemical nature, and after-glow brightness is high, remaining
The advantages such as brightness time length, but the problem still suffering from poor water resistance.In order to solve this problem, stable chemical nature, resistance to water are better than
The silicate systems of aluminate becomes the focus of the exploitation of long-afterglow material in the last few years, but this system afterglow intensity and lasting time
Between still have much room for improvement.Further, the long after glow luminous material the most developed, it appeared that afterglow center major part is all concentrated
At Eu2+, this makes without Eu2+The long-afterglow material of function admirable be still the demand of exploitation.
The open a kind of green long afterglow luminescent material of Chinese patent CN104927851A, its molecular formula is: Ca2-xSnO4: Erx,
B0.05, wherein: x=0.005～0.05.Additionally provide the preparation method of above-mentioned green long afterglow luminescent material, by mass percentage
Weigh CaCO3、SnO2、Er2O3And H3BO3, after being fully ground mix homogeneously, cross 180～220 mesh sieves, the mixed powder obtained
Calcine after body tabletting, naturally cool to room temperature, ground 180～220 mesh sieves, prepare green long afterglow luminescent material.Warp
Crossing ultraviolet excitation, sample sends bright green after-glow light, and the main emission peak of emission spectrometry is positioned near 552nm；Remove
After removing ultraviolet light, sample has obvious green long afterglow characteristic, and twilight sunset naked eyes are visible.
Chinese patent CN100463950C discloses the inverse spinel structure magnesium stannate green that a kind of transition metal divalent manganesetion activates
Long lad phosphor and being prepared as: Mg2SnO4:Mn2+, Mg2SnO4For substrate, Mn2+It is active ions.And SnO MgO)2
Making substrate, dopant ion is Mn2+, with manganese oxalate (Mn (CH3COO)2·4H2O) adding, dopant dose is 0.005-1% mole.
MgO and SnO is taken by 2: 1 mol ratios2, weigh activator mixing by 0.005-1% mole and be placed in crucible, calcination temperature
950-1250 DEG C, 1-3 hour response time.Activated carbon makees reducing agent.Reactant is come out of the stove, and in air, cooling obtains subalbous
Through 254nm ultra violet lamp, product, sees that green long afterglow is launched, works as Mn2+Illumination effect when doping is between 0.2-0.3%
Preferably, chromaticity coordinates is x=0.0875, y=0.6083.
At present, the host material with Ca, Sc as cation has no long-persistence luminous document report, also has no afterglowing material field
Patent application.
Summary of the invention
Present invention aims to the problems referred to above that existing long-afterglow material exists, it is provided that synthetic method is simple, afterglow
The Eu that center is not common2+But Ce3+, a kind of green long afterglow luminescent material that afterglow is stronger and preparation method thereof.
The chemical composition formula of described green long afterglow luminescent material is aCaO bSc2O3·cCeO2, wherein, 0.5≤a≤1,0.8
≤ b≤1.2,0.001≤c≤0.1.
The scope of described a, b, c can be 0.75≤a≤0.95,1≤b≤1.1,0.005≤c≤0.05.
The preparation method of described green long afterglow luminescent material, comprises the following steps:
1) weigh the oxide of each component or corresponding salt by the mole ratio of a, b, c, grind and mix homogeneously；
2) pre-burning in air atmosphere, is cooled to regrinding mixing after room temperature；
3) sinter under reducing atmosphere, pulverize after cooling, obtain green long afterglow luminescent material.
In step 1) in, described corresponding salt is selected from the one in nitrate, oxalates, carbonate etc..
In step 2) in, the temperature of described pre-burning can be 500～800 DEG C, and the time of pre-burning can be 2～6h.
In step 3) in, described reducing atmosphere can be the mixing of CO (carbon monoxide converter) gas, pure hydrogen, ammonia or nitrogen and hydrogen
Gas；The temperature of described sintering can be 1100～1600 DEG C, and the time of sintering can be 2～16h.
Compared with prior art, the concrete technique effect highlighted below of the present invention:
1) green long afterglow material of the present invention is basic matrix element with Ca, Sc, O, with Ce3+For afterglow center,
And by increasing trap (for energy storage and the long-persistence luminous) number of host material self, it is achieved that long-persistence luminous intensity
Regulation.
2) green long afterglow materials synthesis of the present invention is simple, afterglow intensity is high, and need not to introduce in the defect of other energy storage
The heart, after ultraviolet-visible photoirradiation, has strong green long afterglow luminous seen from naked eyes.
Accompanying drawing explanation
Fig. 1 is the Ce that embodiment 5 produces3+The room temperature after-glow light spectrogram of doping green long afterglow luminescent material；
Fig. 2 is the Ce that embodiment 5 produces3+The thermoluminescence spectrogram of doping green long afterglow luminescent material.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described, but embodiments of the present invention is not limited in any way.
Comparative example 1:0.95CaO Sc2O3·0.05Eu2O3The synthesis of long-afterglow material
Weigh the Sc of CaO, 2.7584g of 1.0655g2O3Eu with 0.352g2O3, it is fully ground in agate mortar and mixes
After closing uniformly, sintering in two steps: first, at 500 DEG C of presintering 4h of lower temperature, it is cooled to room temperature, takes out and be again fully ground
And mix homogeneously, 1100 DEG C of sintering 16h under carbon monoxide atmosphere.Sample is taken out and grinds, finally give sample, through ultraviolet
After light irradiates to blue light light, sample has no any long afterglow emission phenomena.
Embodiment 1:0.5CaO 1.1Sc2O3·0.05CeO2The synthesis of long-afterglow material
Weigh the Sc of CaO, 3.0342g of 0.5608g2O3With 0.4883 Ce (NO)3·6H2O, in agate mortar fully
Grind and after mix homogeneously, in two steps sintering: first, at 500 DEG C of presintering 4h of lower temperature, be cooled to room temperature, take out again
It is fully ground and mix homogeneously, 1100 DEG C of sintering 16h under carbon monoxide atmosphere.Sample is taken out and grinds, finally give sample,
After ultraviolet light to blue light light irradiates, electromagnetic radiation goes out stronger green long afterglow.
Embodiment 2:0.65CaO 0.8Sc2O3·0.07CeO2The synthesis of long-afterglow material
Weigh the CaC of 0.2252g2O4·H2The Sc of O, 0.3004g2O3Sedemesis. hydrate with 0.0088g
Ce2(C2O4)3·xH2O, is fully ground and after mix homogeneously, in two steps sintering: first, lower temperature 550 DEG C in agate mortar
Presintering 6h, is cooled to room temperature, takes out and is again fully ground and mix homogeneously, 1250 DEG C of sintering 12h under carbon reduces.By sample
Taking out and grind, finally give sample, after ultraviolet light to blue light light irradiates, electromagnetic radiation goes out stronger green long afterglow.
Embodiment 3:0.75CaO 0.95Sc2O3·0.1CeO2The synthesis of long-afterglow material
Weigh the Ca (NO of 0.7084g3)2·4H2The Sc of O, 0.3004g2O3CeO with 0.0373g2, fill in agate mortar
Divide and grind and after mix homogeneously, in two steps sintering: first, at 600 DEG C of presintering 5h of lower temperature, be cooled to room temperature, take out again
Secondary it is fully ground and mix homogeneously, 1300 DEG C of sintering 9h under the mixed atmosphere of hydrogen and nitrogen.Sample is taken out and grinds, finally
Obtaining sample, after ultraviolet light to blue light light irradiates, electromagnetic radiation goes out stronger green long afterglow.
Embodiment 4:0.85CaO 1.2Sc2O3·0.001CeO2The synthesis of long-afterglow material
Weigh the CaCO of 0.4003g3, the Sc of 0.0528g2O3Ce (NO) with 0.0559g3·6H2O, fills in agate mortar
Divide and grind and after mix homogeneously, in two steps sintering: first, at 750 DEG C of presintering 4h of lower temperature, be cooled to room temperature, take out again
Secondary it is fully ground and mix homogeneously, 1450 DEG C of sintering 6h under the mixed atmosphere of hydrogen and nitrogen.Sample is taken out and grinds, finally
Obtaining sample, after ultraviolet light to blue light light irradiates, electromagnetic radiation goes out stronger green long afterglow.
Embodiment 5:0.95CaO Sc2O3·0.01CeO2The synthesis of long-afterglow material
Weigh the CaCO of 0.6005g3, the Sc of 0.3004g2O3CeO with 0.1760g2, it is fully ground also in agate mortar
After mix homogeneously, sintering in two steps: first, at 650 DEG C of presintering 2h of lower temperature, it is cooled to room temperature, takes out and the most fully grind
Mill mix homogeneously, 1550 DEG C of sintering 4h under the argon mixed atmosphere with hydrogen.Sample is taken out and grinds, finally give sample,
After ultraviolet light to blue light light irradiates, electromagnetic radiation goes out stronger green long afterglow.
The Ce that embodiment 5 produces3+The room temperature after-glow light spectrogram of doping green long afterglow luminescent material sees Fig. 1；Embodiment 5 is raw
The Ce produced3+The thermoluminescence spectrogram of doping green long afterglow luminescent material sees Fig. 2.
Embodiment 6:CaO 1.15Sc2O3·0.03CeO2The synthesis of long-afterglow material
Weigh the Sc of CaO, 0.0018g of 0.4767g2O3Ce with 0.0019g2(C2O4)3·2H2O, fills in agate mortar
Divide and grind and after mix homogeneously, in two steps sintering: first, at 800 DEG C of presintering 2h of lower temperature, be cooled to room temperature, take out again
Secondary it is fully ground and mix homogeneously, 1600 DEG C of sintering 2h under ammonia atmosphere.Sample is taken out and grinds, finally give sample, warp
After ultraviolet light irradiates to blue light light, electromagnetic radiation goes out stronger green long afterglow.
The green long afterglow luminescent material that the present invention provides can be excited by ultraviolet-visible light, after stopping exciting light irradiation, it is possible to produces
The green broadband that stronger main peak is positioned at 515nm is long-persistence luminous.
Claims (7)
1. a green long afterglow luminescent material, it is characterised in that its chemical composition formula is aCaO bSc2O3·cCeO2, wherein,
0.5≤a≤1,0.8≤b≤1.2,0.001≤c≤0.1.
2. a kind of green long afterglow luminescent material, it is characterised in that described a, b, c are in the range of 0.75
≤ a≤0.95,1≤b≤1.1,0.005≤c≤0.05.
The preparation method of a kind of green long afterglow luminescent material the most as claimed in claim 1, it is characterised in that comprise the following steps:
1) weigh the oxide of each component or corresponding salt by the mole ratio of a, b, c, grind and mix homogeneously；
2) pre-burning in air atmosphere, is cooled to regrinding mixing after room temperature；
3) sinter under reducing atmosphere, pulverize after cooling, obtain green long afterglow luminescent material.
The preparation method of a kind of green long afterglow luminescent material the most as claimed in claim 3, it is characterised in that in step 1) in,
Described corresponding salt one in nitrate, oxalates, carbonate.
The preparation method of a kind of green long afterglow luminescent material the most as claimed in claim 3, it is characterised in that in step 2) in,
The temperature of described pre-burning is 500～800 DEG C, and the time of pre-burning is 2～6h.
The preparation method of a kind of green long afterglow luminescent material the most as claimed in claim 3, it is characterised in that in step 3) in,
Described reducing atmosphere is the gaseous mixture of CO (carbon monoxide converter) gas, pure hydrogen, ammonia or nitrogen and hydrogen.
The preparation method of a kind of green long afterglow luminescent material the most as claimed in claim 3, it is characterised in that in step 3) in,
The temperature of described sintering is 1100～1600 DEG C, and the time of sintering is 2～16h.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1981018A (en) * | 2004-06-30 | 2007-06-13 | 三菱化学株式会社 | Fluorescent substance, light-emitting element using the same, image display device, and illuminating device |
| EP1901262A1 (en) * | 2005-06-30 | 2008-03-19 | Japan Science and Technology Agency | Phosphorescent material, process for producing the same, and phosphorescent display element |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1981018A (en) * | 2004-06-30 | 2007-06-13 | 三菱化学株式会社 | Fluorescent substance, light-emitting element using the same, image display device, and illuminating device |
| EP1901262A1 (en) * | 2005-06-30 | 2008-03-19 | Japan Science and Technology Agency | Phosphorescent material, process for producing the same, and phosphorescent display element |
Non-Patent Citations (1)
| Title |
|---|
| YASUO SHIMOMURA等: "Photoluminescence and Crystal Structure of Green-Emitting Phosphor CaSc2O4:Ce3+", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》 * |
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Inventor after: Li Ye Inventor after: Liu Wu Inventor after: Zhou Tianliang Inventor after: Zhuang Yixi Inventor before: Jie Rongjun Inventor before: Li Ye Inventor before: Liu Wu Inventor before: Zhou Tianliang Inventor before: Zhuang Yixi |
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