CN102719244B - Secondarily-excited type silicon-aluminate long-afterglow fluorescent powder and preparation method thereof - Google Patents

Secondarily-excited type silicon-aluminate long-afterglow fluorescent powder and preparation method thereof Download PDF

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CN102719244B
CN102719244B CN201210209233.3A CN201210209233A CN102719244B CN 102719244 B CN102719244 B CN 102719244B CN 201210209233 A CN201210209233 A CN 201210209233A CN 102719244 B CN102719244 B CN 102719244B
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fluorescent powder
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excited
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CN102719244A (en
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彭玲玲
曹仕秀
韩涛
程小耀
杨小琴
魏宁
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Chongqing DNT technology development limited liability company
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Chongqing University of Arts and Sciences
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Abstract

The invention relates to secondarily-excited type silicon-aluminate long-afterglow fluorescent powder and a preparation method thereof, which belongs to the technical field of luminescent materials. The composition of the fluorescent powder is Sr3+x-aM1-xAl2x-b-cSiO5+4x: aEu<2+>, bDy<3+>, cRE<3+> (M=Ca, Sr, Ba, Zn; RE=Nb, Sm, Tm, Er, Ce, Pr and the like, 0(x(5; 0(a(0.8; 0(b(0.5; 0(c(0.5). The designing idea of the fluorescent powder is that two luminescent centers, i. e. the Eu<2+> and the RE<3+>, exist, the emission spectrum of Eu<2+> is superposed with the excitation spectrum of the RE<3+>, and energy transfer exists between the Eu<2+> and the RE<3+>; the Eu<2+> is excited to emit light by external incident light, and the RE<3+> is then excited to emit the light by the emitted light of the Eu<2+> to form secondarily-excited type emitted light; the color of the emitted light is determined by the concentration ratio of the Eu<2+> to the RE<3+>; and the afterglow time of progressively-excited type fluorescent powder is determined by the proportion of the Eu<2+> and the Dy<3+>. The related preparation method comprises the following steps of: weighing all kinds of oxide raw materials according to the measuring ratio of all elements, adding a fluxing agent, placing and calcining under a reducing atmosphere after uniformly mixing through ball milling, and crushing and sieving a product to obtain the required fluorescent powder. The secondarily-excited type fluorescent powder can emit green, red and even white fluorescent light, and the afterglow time can reach 8-12 hours.

Description

A kind of secondary excitation type silicon-aluminate long-afterglow fluorescent powder and preparation method thereof
Technical field
The invention belongs to luminescent material technical field, relate to a kind of secondary excitation type long after glow luminous material, the invention still further relates to the preparation method of this luminescent material.
Background technology
Long after glow luminous material is commonly called as noctilucent material, belonging to is the one of embedded photoluminescent material, under sunlight, luminescent lamp, incandescent light etc. irradiate, can absorb the energy in light, and by the energy storage of absorption in the material, then with the energy slow releasing that the form of luminescence will store.Long after glow luminous material has been widely used in the fields such as emergent indicating equipment, low light illuminant, industrial art, information storage and energetic ray detection.At present, blue-greenish colour and the mainly rare earth doped aluminate of yellow-green colour long-afterglow material and silicate, this two classes material all increases than the long-afterglow material of traditional sulfide systems in luminosity, time of persistence, chemical stability, and its performance has reached practical application to be needed and realize suitability for industrialized production.But this two classes long after glow luminous material receives the single restriction of the color development of material own, is difficult to the needs meeting multicolor.Current red long afterglow material mainly comprises rear-earth-doped alkaline earth sulfide, oxysulfide, titanates of alkali-earth metals system and phosphate system.The twilight sunset of the red long afterglow material of sulfur-bearing and brightness are better, but poor chemical stability, application is restricted.Alkaline earth titanate system red long afterglow luminous material luminosity is low, time of persistence is short.Phosphate system red long afterglow material with low cost, but preparation needs reducing atmosphere to protect mostly, complex process.Therefore, the long after glow luminous material that development stable in properties, afterglow property are good, with low cost is still needed now.
The long after glow luminous material of current acquisition practical application, mainly Sr 2mgSi 2o 7: Eu 2+, Dy 3+; CaAl 2o 4: Eu 2+, Nd 3+deng blue light long-afterglow material, SrAl 2o 4: Eu 2+, Dy 3+; SrAl 4o 7: Eu 2+, Dy 3+; CaAl 4o 7: Tb 3+, Ce 3+; Sr 4al 14o 25: Eu 2+, Dy 3+deng blue green light long-afterglow material, Y 2o 2s:Eu 3+, Ln 3+ruddiness long-afterglow material, and traditional sulfide and alkaline earth sulfide long-afterglow material.Therefore, still need the long after glow luminous material that development color is enriched more, development of new high-performance long after glow luminous material is necessary.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, silicon-aluminate long-afterglow fluorescent powder of a kind of secondary excitation type and preparation method thereof is provided.The present invention adopts solid state reaction legal system for long persistence luminescent powder Sr 3+x-am 1-xal 2x-b-csiO 5+4x: aEu 2+, bDy 3+, cRE 3+(M=Ca, Sr, Ba, Zn; RE=Nb, Sm, Tm, Er, Ce, Pr etc.), the method operating procedure is easy, light-emitting phosphor and afterglow property good.
Secondary excitation type fluorescent material of the present invention is achieved through the following technical solutions, and consists of Sr 3+x-am 1-xal 2x-b-csiO 5+4x: aEu 2+, bDy 3+, cRE 3+(M=Ca, Sr, Ba, Zn; RE=Nb, Sm, Tm, Er, Ce, Pr etc., 0<x<5; 0<a<0.8; 0<b<0.5; 0<c<0.5).The mentality of designing of this fluorescent material is existence two luminescence center, Eu 2+and RE 3+, Eu 2+emmission spectrum and RE 3+excitation spectrum overlapping, Eu 2+and RE 3+between there is transmission ofenergy; Extraneous incident light excites Eu 2+luminescence, Eu 2+utilizing emitted light excite RE again 3+luminescence, forms secondary excitation type luminous; Eu 2+and RE 3+concentration ratio determine radiative color; Eu 2+and Dy 3+ratio determine time of persistence of secondary excitation type fluorescent material.Concrete steps are as follows:
(1) according to structural formula Sr 3+x-am 1-xal 2x-b-csiO 5+4x: aEu 2+, bDy 3+, cRE 3+(M=Ca, Sr, Ba, Zn; RE=Nb, Sm, Tm, Er, Ce, Pr etc.) take SrCO respectively in molar ratio 3, M 2o 3, Al 2o 3, SiO 2, REO 2or RE 2o 3, Eu 2o 3and Dy 2o 3;
(2) take the fusing assistant of above medicine total mass 0.001wt% ~ 10.0wt% more respectively, fusing assistant is H 3bO 3, BaF 2, CaF 2, SrF 2in at least one;
(3) raw material and fusing assistant is even by ground and mixed, under reducing atmosphere 1000 DEG C ~ 1600 DEG C, calcination time is 3 ~ 8h, obtains target product.
In the present invention, described reducing atmosphere is provided by activated carbon powder, carbon black combustion method, or uses nitrogen/hydrogen mixed gas.
Compared with prior art, tool of the present invention has the following advantages:
1, the present invention proposes the thinking of secondary excitation, by utilizing the transmission ofenergy between luminescence center to realize secondary excitation type continuous illumination, adopt new mentality of designing, compared with traditional long persistence luminescent powder for preparing long persistence luminescent powder, color is abundanter, can transmitting green to red fluorescence.
2, the fluorescent material brightness prepared of the present invention is high, crystallinity and afterglow property good, there is good circulation ratio.
3, preparation method of the present invention is simple, easy handling, cost are low.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the preparation method of the long persistence luminescent powder of secondary excitation type provided by the present invention;
Fig. 2 is Sr of the present invention 3.94al 1.995siO 9: 0.06Eu 2+, 0.005Dy 3+x-ray diffraction spectrogram;
Fig. 3 is Sr of the present invention 3.94al 1.995siO 9: 0.06Eu 2+, 0.005Dy 3+excitation and emission spectra figure.
Embodiment
Embodiment 1
According to structural formula Sr 3.94al 1.994siO 9: 0.06Eu 2+, 0.006Dy 3+take SrCO respectively 3(A.R.) 3.94mol, Al 2o 3(A.R.) 0.997mol, SiO 2(A.R.) 1mol, Eu 2o 3(A.R.) 0.03mol and Dy 2o 3(A.R.) 0.003mol, then the fusing assistant H taking above medicine total mass 5wt% respectively 3bO 3; Mixed by the above-mentioned raw material taken, then calcine under activated carbon powder burning provides reducing atmosphere, calcining temperature is 1400 DEG C, and calcination time is 8h, obtains target product.
Embodiment 2
According to structural formula Sr 2.94caAl 1.994siO 9: 0.06Eu 2+, 0.006Nb 3+take SrCO respectively 3(A.R.) 2.94mol, CaCO 31mol, Al 2o 3(A.R.) 0.997mol, SiO 2(A.R.) 1mol, Eu 2o 3(A.R.) 0.03mol and Nb 2o 3(A.R.) 0.003mol, then the fusing assistant BaF taking above medicine total mass 3wt% respectively 2; The above-mentioned raw material taken is mixed, then at H 2-N 2calcine under (volume ratio 5:95) reducing atmosphere, calcining temperature is 1420 DEG C, and calcination time is 8h, obtains target product.
Embodiment 3
According to structural formula Sr 2.94caAl 1.994siO 9: 0.06Eu 2+, 0.005Dy 3+take SrCO respectively 3(A.R.) 2.94mol, CaCO 31mol, Al 2o 3(A.R.) 0.997mol, SiO 2(A.R.) 1mol, Eu 2o 3(A.R.) 0.03mol and Dy 2o 3(A.R.) 0.003mol, then the fusing assistant CaF taking above medicine total mass 0.5wt% respectively 2; The above-mentioned raw material taken is mixed, then at H 2-N 2calcine under (volume ratio 10:90) reducing atmosphere, calcining temperature is 1420 DEG C, and calcination time is 8h, obtains target product.
Embodiment 4
According to structural formula Sr 2.94baAl 1.994siO 9: 0.06Eu 2+, 0.006Dy 3+take SrCO respectively 3(A.R.) 2.94mol, BaCO 31mol, Al 2o 3(A.R.) 0.997mol, SiO 2(A.R.) 1mol, Eu 2o 3(A.R.) 0.03mol and Dy 2o 3(A.R.) 0.003mol, then the fusing assistant H taking above medicine total mass 1wt% respectively 3bO 3with the fusing assistant BaF2 of 1wt%; Mixed by the above-mentioned raw material taken, then calcine under activated carbon powder burning provides reducing atmosphere, calcining temperature is 1420 DEG C, and calcination time is 8h, obtains target product.
Embodiment 5
According to structural formula Sr 2.94baAl 1.94siO 9: 0.06Eu 2+, 0.06Ce 3+take SrCO respectively 3(A.R.) 2.94mol, BaCO 31mol, Al 2o 3(A.R.) 0.97mol, SiO 2(A.R.) 1mol, Eu 2o 3(A.R.) 0.03mol and CeO 2(A.R.) 0.06mol, then the fusing assistant H taking above medicine total mass 5wt% respectively 3bO 3with the fusing assistant BaF of 0.1wt% 2; Mixed by the above-mentioned raw material taken, then calcine under activated carbon powder burning provides reducing atmosphere, calcining temperature is 1420 DEG C, and calcination time is 8h, obtains target product.
Embodiment 6
Sr 2.94baAl 1.934siO 9: 0.06Eu 2+, 0.06Ce 3+, 0.006Dy 3+take SrCO respectively 3(A.R.) 2.94mol, BaCO 31mol, Al 2o 3(A.R.) 0.967mol, SiO 2(A.R.) 1mol, Eu 2o 3(A.R.) 0.03mol CeO 2(A.R.) 0.06mol and Dy 2o 3(A.R.) 0.003mol, then the fusing assistant H taking above medicine total mass 0.5wt% respectively 3bO 3with the fusing assistant BaF of 3wt% 2; The above-mentioned raw material taken is mixed, then at H 2-N 2calcine under (volume ratio 5:95) reducing atmosphere, calcining temperature is 1420 DEG C, and calcination time is 8h, obtains target product.

Claims (3)

1. a secondary excitation type silico-aluminate fluorescent material, what it is characterized in that fluorescent material consists of Sr 3+x-am 1-xal 2x-b-csiO 5+4x: aEu 2+, bDy 3+, cRE 3+(M=Ca, Sr, Ba, Zn; RE=Nb, Sm, Tm, Er, Ce, Pr etc., 0<x<5; 0<a<0.8; 0<b<0.5; 0<c<0.5).
2. the preparation method of fluorescent material as claimed in claim 1, it is characterized in that the method is the fluorescent material using high temperature solid-state method synthesis secondary excitation type, concrete steps are as follows:
(1) according to structural formula Sr 3+x-am 1-xal 2x-b-csiO 5+4x: aEu 2+, bDy 3+, cRE 3+, take SrCO respectively in molar ratio 3, M 2o 3, Al 2o 3, SiO 2, REO 2or RE 2o 3, Eu 2o 3and Dy 2o 3;
(2) take the fusing assistant of above medicine total mass 0.001 wt% ~ 10.0 wt% more respectively, fusing assistant is H 3bO 3, BaF 2, CaF 2, SrF 2in at least one;
(3) raw material and fusing assistant is even by ground and mixed, under reducing atmosphere 1000 DEG C ~ 1600 DEG C, calcination time is 3 ~ 8 h, obtains target product.
3. the preparation method of fluorescent material as claimed in claim 2, is characterized in that described in step (3), reducing atmosphere is provided by activated carbon powder, carbon black combustion method, or uses nitrogen/hydrogen mixed gas.
CN201210209233.3A 2012-06-25 2012-06-25 Secondarily-excited type silicon-aluminate long-afterglow fluorescent powder and preparation method thereof Active CN102719244B (en)

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CN103013503A (en) * 2012-12-22 2013-04-03 广州有色金属研究院 Silicate fluorescent material
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CN109988568A (en) * 2019-04-08 2019-07-09 北京科技大学 A kind of nitrogen oxides green long afterglow luminescent material and preparation method thereof

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Tunable afterglow color in Eu2+ and Dy3+ co-activated alkaline earth feldspar solid solutions phosphors;Zhiyu Wang等;《Journal of Luminescence》;20050417;第124卷;试验部分 *

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